Method for producing cyclic imide compound, composition, and compound

ABSTRACT

A first object of the present invention is to provide a method for producing a cyclic imide compound with high yield and high purity. A second object of the present invention is to provide a composition that can be used in the method for producing a cyclic imide compound with high yield and high purity. A third object of the present invention is to provide an intermediate compound that can be used in the method for producing a cyclic imide compound with high yield and high purity. The method for producing a cyclic imide compound according to the present invention includes reacting a compound represented by formula (1) below with at least one amine compound to obtain a compound represented by formula (2) below.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Divisional of U.S. patent application Ser. No.17/655,293 filed on Mar. 17, 2022, which is a Continuation of PCTInternational Application No. PCT/JP2020/033541 filed on Sep. 4, 2020,which claims priority under 35 U.S.C. § 119(a) to Japanese PatentApplication No. 2019-171333 filed on Sep. 20, 2019. The aboveapplication is hereby expressly incorporated by reference, in itsentirety, into the present application.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to a method for producing a cyclic imidecompound, a composition, and a compound.

2. Description of the Related Art

It has been studied that organic thin film transistors (organic TFTs)having organic semiconductor films (organic semiconductor layers) areused in, for example, field effect transistors (FETs) for liquid crystaldisplays and organic electric luminescence (EL) displays and apparatuseswith a logic circuit including a radio frequency identifier (RFID, RFtag) and a memory because weight reduction, cost reduction, and highflexibility can be achieved.

JP2018-6745A discloses a cyclic imide compound including an azaperyleneskeleton as an organic semiconductor compound for forming such anorganic semiconductor film.

SUMMARY OF THE INVENTION

As a result of studies conducted on the method for producing a cyclicimide compound including an azaperylene skeleton disclosed inJP2018-6745A, the present inventors have found that there is room forfurther improvement in yield and purity.

Accordingly, it is an object of the present invention to provide amethod for producing a cyclic imide compound with high yield and highpurity.

It is another object of the present invention to provide a compositionthat can be used in a method for producing a cyclic imide compound withhigh yield and high purity.

It is also another object of the present invention to provide anintermediate compound that can be used in a method for producing acyclic imide compound with high yield and high purity.

As a result of thorough studies to achieve the above objects, thepresent inventors have found that the above objects can be achieved by acertain production method, and have completed the present invention.

That is, the present inventors have found that the above objects can beachieved by the following configurations.

[1] A method for producing a cyclic imide compound includes reacting acompound represented by formula (1) described later with at least oneamine compound to obtain a compound represented by formula (2) describedlater.

[2] The method for producing a cyclic imide compound according to [1]includes:

-   -   a step Y1 of reacting the compound represented by the        formula (1) with a first amine compound represented by        formula (3) described later to obtain a compound represented by        formula (4) described later;    -   a step Y2 of reacting the compound represented by the        formula (4) with a second amine compound represented by        formula (5) described later to obtain a compound represented by        formula (6) described later;    -   a step Y3 of removing P³¹ serving as a protecting group from the        compound represented by the formula (6) to obtain a compound        represented by formula (7) described later; and    -   a step Y4 of obtaining the compound represented by the        formula (2) from the compound represented by the formula (7).

[3] In the method for producing a cyclic imide compound according to [1]or [2], the compound represented by the formula (1) is a compoundrepresented by formula (8) described later, and the compound representedby the formula (2) is a compound represented by formula (9) describedlater.

[4] In the method for producing a cyclic imide compound according to[3], the compound represented by the formula (8) is a compoundrepresented by formula (10) described later.

[5] In the method for producing a cyclic imide compound according to[4], the compound represented by the formula (10) is a compoundrepresented by formula (10′) described later.

[6] In the method for producing a cyclic imide compound according to[5], X¹¹¹ to X¹¹⁶ represent a chlorine atom.

[7] The method for producing a cyclic imide compound according to [3]includes:

-   -   a step Y1′ of reacting a compound represented by formula (X1)        described later with a compound represented by formula (X2)        described later to obtain a composition including a compound        represented by formula (11A) described later and a compound        represented by formula (11B) described later, and then reacting        the composition with a first amine compound represented by        formula (12) described later without subjecting the composition        to column purification to obtain a compound represented by        formula (13) described later;    -   a step Y2′ of reacting the compound represented by the        formula (13) with a second amine compound represented by        formula (14) described later to obtain a compound represented by        formula (15) described later;    -   a step Y3′ of removing P³¹ serving as a protecting group from        the compound represented by the formula (15) to obtain a        compound represented by formula (16) described later; and    -   a step Y4′ of obtaining the compound represented by the        formula (9) from the compound represented by the formula (16).

[8] The method for producing a cyclic imide compound according to [1]includes a step of reacting a compound represented by formula (X1)described later with a compound represented by formula (X2) describedlater to obtain a composition including a compound represented byformula (11A) described later and a compound represented by formula(11B) described later, and then reacting the composition with an aminecompound represented by formula (14) described later without subjectingthe composition to column purification to obtain a compound representedby formula (9′) described later.

[9] The method for producing a cyclic imide compound according to [7] or[8] further includes a step Y0′ of purifying the compound represented bythe formula (X2) before reacting the compound represented by the formula(X1) with the compound represented by the formula (X2).

[10] A composition used for synthesizing a compound represented byformula (9) described later includes at least a compound represented byformula (8) described later.

In the composition, a total content of a compound represented by formula(17) described later and a compound represented by formula (18)described later is 3.0 mass % or less relative to a total solid contentof the composition.

[11] A compound is represented by formula (4) described later.

[12] A compound is represented by formula (6) described later.

[13] A compound is represented by formula (7) described later.

[14] A compound is represented by formula (11A′) described later.

[15] A compound is represented by formula (11A″) described later.

According to the present invention, a method for producing a cyclicimide compound with high yield and high purity can be provided.

According to the present invention, a composition that can be used inthe method for producing a cyclic imide compound with high yield andhigh purity can be provided.

According to the present invention, an intermediate compound that can beused in the method for producing a cyclic imide compound with high yieldand high purity can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a sectional view schematically illustrating a structure of abottom gate-bottom contact organic thin film transistor, which is anexample of organic thin film transistors;

FIG. 2 is a sectional view schematically illustrating a structure of abottom gate-bottom contact organic thin film transistor, which isanother example of organic thin film transistors;

FIGS. 3A to 3C are schematic views illustrating an example of a methodfor forming an organic semiconductor film of an organic thin filmtransistor;

FIGS. 4A to 4D are schematic views for illustrating another example of amethod for forming an organic semiconductor film of an organic thin filmtransistor;

FIGS. 5A to 5C are schematic views for illustrating another example of amethod for forming an organic semiconductor film of an organic thin filmtransistor; and

FIG. 6 is a schematic view illustrating an example of a substrate and amember used in a method for forming an organic semiconductor film of anorganic thin film transistor.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereafter, the method for producing a cyclic imide compound, thecomposition, and the compound according to embodiments of the presentinvention will be described in detail. The following descriptions ofconstituent elements may be made based on representative embodiments ofthe present invention. However, the present invention is not limited tosuch embodiments.

In this specification, every numerical range expressed using “to” meansa range including numerical values before and after “to” as the lowerand upper limits.

In this specification, (meth)acryloyl means acryloyl or methacryloyl.

In this specification, the expression of a compound includes not onlythe compound itself, but also a salt thereof and an ion thereof.Compounds whose structure is partly modified are also included as longas the intended effects are not impaired.

Compounds whose substitution or unsubstitution is not explicitly statedmay have a substituent as long as the intended effects are not impaired.The same applies to a substituent, a linking group, and the like(hereafter referred to as a substituent and the like).

In this specification, when a plurality of substituents and the like arerepresented by a particular symbol or when a plurality of substituentsand the like are simultaneously defined, the substituents and the likemay be the same as or different from each other unless otherwisespecified. The same also applies to the definition of the number ofsubstituents and the like. When a plurality of substituents and the likeare close (particularly adjacent) to each other, they may be linked toeach other to form a ring unless otherwise specified.

In this specification, examples of the halogen atom include a fluorineatom, a chlorine atom, a bromine atom, and an iodine atom.

In the present invention, when a group can form an acyclic skeleton anda cyclic skeleton, the group includes a group having an acyclic skeletonand a group having a cyclic skeleton unless otherwise specified.

For example, aliphatic hydrocarbon groups, alkyl groups, alkenyl groups,and alkynyl groups include groups having any of linear, branched, andcyclic structures unless otherwise specified.

More specific examples of the alkyl group include a linear alkyl group,a branched alkyl group, and a cyclic (cyclo) alkyl group.

When the group can form a cyclic skeleton, the lower limit of the numberof atoms of the group forming a cyclic skeleton is 3 or more andpreferably 5 or more regardless of the lower limit of the number ofatoms specifically described for this group. Examples of the cycloalkylgroup include a bicycloalkyl group and a tricycloalkyl group.

Method for Producing Cyclic Imide Compound

A method for producing a cyclic imide compound according to anembodiment of the present invention (hereafter also referred to as “aproduction method according to an embodiment of the present invention”)is a production method in which a compound represented by formula (1)described later is reacted with at least one amine compound to obtain acompound represented by formula (2) described later.

The present inventors have studied a method for producing a cyclic imidecompound including an azaperylene skeleton, such as a compoundrepresented by formula (2). As a result, they have found that the factorthat does not satisfy a desired level of yield and purity in theproduction method of the related art is formation of a target cyclicimide compound via an acid anhydride intermediate. Specifically, an acidanhydride including an azaperylene skeleton has considerably lowsolubility in a solvent and thus is poor in terms of ease of handlingand quality control, which is considered to decrease the yield andpurity when an acid anhydride intermediate including an azaperyleneskeleton is modified into a cyclic imide structure to synthesize atarget cyclic imide compound.

On the other hand, the present inventors have lately found a novelmethod for producing a cyclic imide compound without using an acidanhydride intermediate. In the production method according to anembodiment of the present invention, a cyclic imide compound includingan azaperylene skeleton, such as a compound represented by formula (2),can be produced in high yield and high purity. Hereafter, the productionmethod according to an embodiment of the present invention will bedescribed in detail.

The production method according to an embodiment of the presentinvention includes a step of reacting a compound represented by formula(1) below with at least one amine compound to obtain a compoundrepresented by formula (2) below.

First, the compound represented by the formula (1) and serving as a rawmaterial, the compound represented by the formula (2) and serving as anintended product, and the amine compound will be described.

Compound Represented by Formula (1)

In the formula (1), A¹¹ to A¹⁸ each independently represent —N═ or—C(R¹⁵)═.

At least one of A¹¹ to A¹⁸ represents —N═. In particular, preferably oneto four of A¹¹ to A¹⁸ represent —N═, more preferably one to three of A¹¹to A¹⁸ represent —N═, further preferably one or two of A¹¹ to A¹⁸represent —N═, and particularly preferably two of A¹¹ to A¹⁸ represent—N═.

The nitrogen atom of —N═ that may be represented by A¹¹ to A¹⁸ may havea substituent. Examples thereof include an N-oxide group (N→O group) anda salt having a counter anion.

R¹⁵ represents a hydrogen atom or a substituent.

The substituent represented by R¹⁵ is not particularly limited, and is,for example, a group selected from the substituent group Z.

Substituent Group Z

The substituent group Z includes a halogen atom, an alkyl group, analkenyl group, an alkynyl group, an aryl group, a heterocyclic group, asilyl group, an alkoxy group, an amino group, an aryloxy group, an acylgroup, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxygroup, an acylamino group, an aminocarbonylamino group, analkoxycarbonylamino group, an aryloxycarbonylamino group, analkylsulfonylamino group, an arylsulfonylamino group, an alkylthiogroup, an arylthio group, an alkylsulfinyl group, an arylsulfinyl group,an alkylsulfonyl group, an arylsulfonyl group, a silyloxy group, aheterocyclic oxy group, a carbamoyl group, a carbamoyloxy group, aheterocyclic thio group, a sulfamoyl group, an arylazo group, aheterocyclic azo group, an imide group, a phosphino group, a phosphinylgroup, a phosphinyloxy group, a phosphinylamino group, a hydrazinogroup, an imino group, a cyano group, a hydroxy group, a nitro group, amercapto group, a sulfo group, a carboxy group, a hydroxamic acid group,a sulfino group, a boronic acid group (—B(OH)₂), a phosphato group(—OPO(OH)₂), a phosphono group (—PO(OH)₂), and a sulfato group (—OSO₃H).

The group selected from the substituent group Z may further have asubstituent.

Examples of the halogen atom included in the substituent group Z includea fluorine atom, a chlorine atom, a bromine atom, and an iodine atom,and a fluorine atom or a chlorine atom is preferable.

The alkyl group included in the substituent group Z is not particularlylimited, but is preferably an alkyl group having 1 (3) to 30 carbonatoms and more preferably an alkyl group having 1 (3) to 20 carbonatoms. The numbers in parentheses represent the number of carbon atomsin the case of cycloalkyl groups.

Examples of the alkyl group that may have a substituent and is includedin the substituent group Z include a methyl group, an ethyl group, apropyl group, a 2-methylpropyl group, a butyl group, an amyl group, apentyl group, a 1-methylpentyl group, a 2,2-dimethylpropyl group, ahexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, anonyl group, a decyl group, a 3,7-dimethyloctyl group, an undecyl group,a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecylgroup, a 2,6-dimethyloctyl group, an icosyl group, a 2-decyltetradecylgroup, a 2-hexyldodecyl group, a 2-ethyloctyl group, a 2-butyldecylgroup, a 1-octylnonyl group, a 2-octyldecyl group, a 2-octyldecyl group,a 7-hexylpentadecyl group, a 2-octyltetradecyl group, a cyclopropylgroup, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, anadamantyl group, a benzyl group, a 2-cyclohexylethyl group, ap-chlorobenzyl group, a 2-phenylethyl group, a trifluoromethyl group, aperfluoroethyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group,C₅F₁₁C₂H₄-, C₆F₁₃C₂H₄-, a 3-aminopropyl group, a 4-aminobutyl group, a5-ethoxypentyl group, a (meth)acryloyloxypropyl group, a(meth)acryloyloxypentyl group, a 4-hydroxybutyl group, a 4-sulfobutylgroup, a 10-phosphonodecyl group, a 2-hydroxyethoxymethyl group, a2-imidazolylethoxymethyl group, a 4-(N,N-dimethylamino)butyl group, anda 5-norbornanemethyl group.

The alkenyl group included in the substituent group Z is notparticularly limited, but is preferably an alkenyl group having 2 to 20carbon atoms, more preferably an alkenyl group having 2 to 12 carbonatoms, and further preferably an alkenyl group having 2 to 8 carbonatoms.

Examples of the alkenyl group that may have a substituent and isincluded in the substituent group Z include a vinyl group, an allylgroup, a 2-butenyl group, a 1-pentenyl group, a 4-pentenyl group, a2-(2-thiazolyl)vinyl group, a 2-(5-thiazolyl)vinyl group, a styrylgroup, and a 2-(2-thienyl)vinyl group.

The alkynyl group included in the substituent group Z is notparticularly limited, but is preferably an alkynyl group having 2 to 20carbon atoms, more preferably an alkynyl group having 2 to 12 carbonatoms, and further preferably an alkynyl group having 2 to 8 carbonatoms.

Examples of the alkynyl group that may have a substituent and isincluded in the substituent group Z include an ethynyl group, apropargyl group, a 1-pentynyl group, a trimethylsilylethynyl group, atriethylsilylethynyl group, a tri-i-propylsilylethynyl group, ap-propylphenylethynyl group, a 2-thienylethynyl group, a2-thiazolylethynyl group, a 5-thiazolylethynyl group, and aphenylethynyl group.

The aryl group included in the substituent group Z is not particularlylimited, but is preferably an aryl group having 6 to 20 carbon atoms andmore preferably an aryl group having 6 to 12 carbon atoms.

Examples of the aryl group that may have a substituent and is includedin the substituent group Z include a phenyl group, a naphthyl group, a2,4,6-trimethylphenyl group, a p-(t-butyl) phenyl group, a4-methyl-2,6-dipropylphenyl group, a 4-fluorophenyl group, a4-trifluoromethylphenyl group, a p-pentylphenyl group, a3,4-dipentylphenyl group, a p-heptoxyphenyl group, and a3,4-diheptoxyphenyl group.

The heterocyclic group included in the substituent group Z is, forexample, a heterocyclic group in which the number of atoms constitutinga ring is three or more, and the atoms constituting the ring areconstituted by at least one heteroatom and 1 to 30 carbon atoms. Theheterocyclic group includes an aromatic heterocyclic group (heteroarylgroup) and an aliphatic heterocyclic group.

Examples of the heteroatom constituting the ring include a nitrogenatom, an oxygen atom, and a sulfur atom. The number of the heteroatomsis not particularly limited, but is, for example, 1 or 2. The number ofcarbon atoms constituting the ring is preferably 3 to 20 and morepreferably 5 to 12.

The heterocyclic group is preferably a five-membered ring or asix-membered ring, or a fused ring of the foregoing.

Examples of the heterocyclic group included in the substituent group Zinclude a thienyl group, a thiazolyl group, an imidazolyl group, apyridyl group, a pyrimidinyl group, a quinolyl group, a furanyl group, aselenophenyl group, a piperidyl group, a morpholino group, abenzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a2-hexylfuranyl group, and a pyranyl group.

The silyl group that may have a substituent and is included in thesubstituent group Z is not particularly limited, but is preferably asilyl group having a group selected from the group consisting of analkyl group and an aryl group as a substituent and having 3 to 40 (morepreferably 3 to 30, and further preferably 3 to 24) carbon atoms.

Examples of the silyl group that may have a substituent and is includedin the substituent group Z include a trimethylsilyl group, atriethylsilyl group, a triphenylsilyl group, a triisopropylsilyl group,and a dimethylphenylsilyl group.

The alkoxy group included in the substituent group Z is not particularlylimited, but is preferably an alkoxy group having 1 to 20 carbon atoms,more preferably an alkoxy group having 1 to 12 carbon atoms, and furtherpreferably an alkoxy group having 1 to 8 carbon atoms.

Examples of the alkoxy group included in the substituent group Z includea methoxy group, an ethoxy group, and a butoxy group.

The amino group that may have a substituent and is included in thesubstituent group Z is not particularly limited, but is preferably anamino group or an amino group having a group selected from the groupconsisting of an alkyl group and an aryl group as a substituent andhaving 1 to 20 (more preferably 1 to 10, and further preferably 1 to 6)carbon atoms.

Examples of the amino group that may have a substituent and is includedin the substituent group Z include an amino group, a methylamino group,a dimethylamino group, a diethylamino group, a dibenzylamino group, andan anilino group.

The aryloxy group included in the substituent group Z is notparticularly limited, but is preferably an aryloxy group having 6 to 20carbon atoms, more preferably an aryloxy group having 6 to 16 carbonatoms, and further preferably an aryloxy group having 6 to 12 carbonatoms.

Examples of the aryloxy group included in the substituent group Zinclude a phenyloxy group and 2-naphthyloxy.

The acyl group included in the substituent group Z is not particularlylimited, but is preferably an acyl group having 1 to 20 carbon atoms,more preferably an acyl group having 1 to 16 carbon atoms, and furtherpreferably an acyl group having 1 to 12 carbon atoms.

Examples of the acyl group that may have a substituent and is includedin the substituent group Z include an acetyl group, a hexanoyl group, abenzoyl group, a formyl group, and a pivaloyl group.

The alkoxycarbonyl group included in the substituent group Z is notparticularly limited, but is preferably an alkoxycarbonyl group having 2to 20 carbon atoms, more preferably an alkoxycarbonyl group having 2 to16 carbon atoms, further preferably an alkoxycarbonyl group having 2 to12 carbon atoms, and particularly preferably a methoxycarbonyl group oran ethoxycarbonyl group.

The aryloxycarbonyl group included in the substituent group Z is notparticularly limited, but is preferably an aryloxycarbonyl group having7 to 20 carbon atoms, more preferably an aryloxycarbonyl group having 7to 16 carbon atoms, further preferably an aryloxycarbonyl group having 7to 10 carbon atoms, and particularly preferably a phenyloxycarbonylgroup.

The acyloxy group included in the substituent group Z is notparticularly limited, but is preferably an acyloxy group having 2 to 20carbon atoms, more preferably an acyloxy group having 2 to 16 carbonatoms, and further preferably an acyloxy group having 2 to 10 carbonatoms.

Examples of the acyloxy group that may have a substituent and isincluded in the substituent group Z include an acetoxy group, abenzoyloxy group, and a (meth)acryloyloxy group.

The acylamino group included in the substituent group Z is notparticularly limited, but is preferably an acylamino group having 2 to20 carbon atoms, more preferably an acylamino group having 2 to 16carbon atoms, and further preferably an acylamino group having 2 to 10carbon atoms.

Examples of the acylamino group included in the substituent group Zinclude an acetylamino group and a benzoylamino group.

The aminocarbonylamino group included in the substituent group Z is notparticularly limited, but is preferably an aminocarbonylamino grouphaving 2 to 20 carbon atoms, more preferably an aminocarbonylamino grouphaving 2 to 16 carbon atoms, further preferably an aminocarbonylaminogroup having 2 to 12 carbon atoms, and particularly preferably a ureidogroup.

The alkoxycarbonylamino group included in the substituent group Z is notparticularly limited, but is preferably an alkoxycarbonylamino grouphaving 2 to 20 carbon atoms, more preferably an alkoxycarbonylaminogroup having 2 to 16 carbon atoms, further preferably analkoxycarbonylamino group having 2 to 12 carbon atoms, and particularlypreferably a methoxycarbonylamino group, a tert-butoxycarbonylaminogroup, an allyloxycarbonylamino group, a2,2,2-trichloroethoxycarbonylamino group, a9-fluorenylmethyloxycarbonylamino group, a2-trimethylsilylethyloxycarbonylamino group, or a benzyloxycarbonylaminogroup.

The aryloxycarbonylamino group included in the substituent group Z isnot particularly limited, but is preferably an aryloxycarbonylaminogroup having 7 to 20 carbon atoms, more preferably anaryloxycarbonylamino group having 7 to 16 carbon atoms, furtherpreferably an aryloxycarbonylamino group having 7 to 12 carbon atoms,and particularly preferably a phenyloxycarbonylamino group.

The alkylthio group included in the substituent group Z is notparticularly limited, but is preferably an alkylthio group having 1 to20 carbon atoms, more preferably an alkylthio group having 1 to 16carbon atoms, and further preferably an alkylthio group having 1 to 12carbon atoms. Examples of the alkylthio group included in thesubstituent group Z include a methylthio group, an ethylthio group, andan octylthio group.

The arylthio group included in the substituent group Z is notparticularly limited, but is preferably an arylthio group having 6 to 20carbon atoms, more preferably an arylthio group having 6 to 16 carbonatoms, further preferably an arylthio group having 6 to 12 carbon atoms,and particularly preferably a phenylthio group.

The above-mentioned group selected from the substituent group Z mayfurther have a substituent. Such a substituent is a group selected fromthe substituent group Z.

In the group further having a substituent (also referred to as a groupformed in combination), the number of substituents that may be furtherincluded is not particularly limited, but is preferably 1 to 6 and morepreferably 1 to 3, for example.

The group formed in combination is not particularly limited, and is, forexample, a group obtained by substituting a group preferable as thegroup selected from the above-described substituent group Z with anothergroup selected from the substituent group Z. Specific examples thereofinclude an alkyl group, an alkenyl group, or an alkynyl group having, asa substituent, a group selected from the group consisting of a halogenatom, an alkyl group, an aryl group, a heterocyclic group (heteroarylgroup), an alkoxy group (including a hydroxyalkoxy group, a halogenatedalkoxy group, and a heteroarylalkoxy group), an amino group, an acyloxygroup, a hydroxy group, a sulfato group, a silyl group, and a phosphonogroup, and an alkynyl group having a halogenated aryl group or a(fluorinated) alkylaryl group as a substituent. A group obtained byremoving one hydrogen atom from the compound represented by the formula(1) can also be employed.

Preferred examples of the group formed in combination include an alkylgroup having a halogen atom as a substituent (halogenated alkyl group),an alkyl group having an aryl group as a substituent, an alkyl grouphaving a heterocyclic group as a substituent, an alkenyl group having anaryl group as a substituent, an alkenyl group having a heterocyclicgroup as a substituent, an alkynyl group having an aryl group as asubstituent, an alkynyl group having a heterocyclic group as asubstituent, an alkyl group having an alkoxy group as a substituent, andan alkynyl group having a silyl group as a substituent.

The substituent represented by R¹⁵ may form a ring. The form in whichthis substituent forms a ring include a form in which substituents arebonded to each other to form a ring and a form in which a plurality ofsubstituents share one atom to form a ring.

The form in which substituents are bonded to each other to form a ringis, for example, a form in which two vinyl groups are bonded to eachother to form a benzene ring together with a carbon atom to which R¹⁵bonds. The form in which a plurality of substituents share one atom toform a ring is, for example, a form in which two substituents arecombined to give a sulfur atom (—S— group).

In particular, R¹⁵ is preferably a hydrogen atom, a halogen atom, acyano group, an alkyl group, an alkenyl group (e.g., an unsubstitutedalkenyl group or an alkenyl group having a silyl group, an aryl group,or a heterocyclic group as a substituent), an alkynyl group (e.g., anunsubstituted alkynyl group or an alkynyl group having a silyl group, anaryl group, or a heterocyclic group as a substituent), an aryl group, aheterocyclic group, a nitro group, an alkoxy group, an alkoxycarbonylgroup, or a carboxy group, and more preferably a hydrogen atom, ahalogen atom, a cyano group, an alkenyl group (e.g., an unsubstitutedalkenyl group or an alkenyl group having a silyl group, an aryl group,or a heterocyclic group as a substituent), an alkynyl group (e.g., anunsubstituted alkynyl group or an alkynyl group having a silyl group, anaryl group, or a heterocyclic group as a substituent), an aryl group, ora heterocyclic group.

R¹¹ to R¹⁴ each independently represent an aliphatic hydrocarbon group,an aryl group, or a heteroaryl group. Herein, one of R¹¹ and R¹⁴represents an aliphatic hydrocarbon group, and the other represents anaryl group or a heteroaryl group. One of R¹² and R¹³ represents analiphatic hydrocarbon group, and the other represents an aryl group or aheteroaryl group. Preferably, R¹² and R¹⁴ represent an aliphatichydrocarbon group and R¹¹ and R¹³ represent an aryl group or aheteroaryl group.

The aliphatic hydrocarbon group represented by R¹¹ to R¹⁴ is notparticularly limited, and may be any of linear, branched, and cyclic.The aliphatic hydrocarbon group may also be saturated or unsaturated.The aliphatic hydrocarbon group may include a heteroatom such as anoxygen atom, a sulfur atom, or a nitrogen atom, or may be halogenated.

In particular, the aliphatic hydrocarbon group represented by R¹¹ to R¹⁴is preferably a linear, branched, or cyclic alkyl group having 1 to 20carbon atoms (preferably 1 to 10 carbon atoms), a linear, branched, orcyclic alkenyl group having 2 to 20 carbon atoms (preferably 2 to 10carbon atoms), or a linear, branched, or cyclic alkynyl group having 2to 20 carbon atoms (preferably 2 to 10 carbon atoms).

When the aliphatic hydrocarbon group represented by R¹¹ to R¹⁴ has 2 ormore carbon atoms, the solubility of the compound represented by theformula (1) is further improved, which provides synthetic advantagessuch as reducing the amount of reaction solvents and causing thereaction at low temperature. In some cases, the yield is improved. Inparticular, the aliphatic hydrocarbon group represented by R¹¹ to R¹⁴ ismore preferably a linear, branched, or cyclic alkyl group having 2 to 20carbon atoms (preferably 2 to 10 carbon atoms).

The number of carbon atoms in the aryl group represented by R¹¹ to R¹⁴is not particularly limited, but is preferably 6 to 20 and morepreferably 6 to 12. The aryl group may have a monocyclic structure or afused ring structure (condensed ring structure) in which two or morerings are fused.

The aryl group is, for example, preferably a phenyl group, a naphthylgroup, or an anthryl group, more preferably a phenyl group or a naphthylgroup, and further preferably a phenyl group.

The number of carbon atoms in the heteroaryl group represented by R¹¹ toR¹⁴ is not particularly limited, but is preferably 3 to 30 and morepreferably 3 to 18.

The heteroaryl group has a heteroatom in addition to carbon atoms andhydrogen atoms. Examples of the heteroatom include a sulfur atom, anoxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, aphosphorus atom, a silicon atom, and a boron atom. A sulfur atom, anoxygen atom, or a nitrogen atom is preferable.

The number of heteroatoms included in the heteroaryl group is notparticularly limited, but is preferably 1 to 10, more preferably 1 to 4,and further preferably 1 or 2.

The number of ring members of the heteroaryl group is not particularlylimited, but is preferably 3 to 8, more preferably 5 to 7, and furtherpreferably 5 or 6. The heteroaryl group may have a monocyclic structureor a fused ring structure in which two or more rings are fused. In thecase of a fused ring structure, an aromatic hydrocarbon ring having noheteroatom (e.g., benzene ring) may be included.

Preferred examples of the heteroaryl group include a furyl group, athienyl group, a thiazolyl group, a pyridyl group, a quinolyl group, anisoquinolyl group, and a carbazolyl group.

The aliphatic hydrocarbon group, aryl group, and heteroaryl grouprepresented by R¹¹ to R¹⁴ may further have a substituent. Thesubstituent is, for example, a group selected from the above-describedsubstituent group Z. Specifically, preferred examples of the substituentinclude an alkyl group, an alkenyl group, an alkynyl group, an arylgroup, a heteroaryl group, an alkoxy group, a thioalkyl group, an acylgroup, —C(═O)NR^(1X)R^(2X), —NR^(3X)C(═O)R^(4X), —S(═O)₂NR^(5X)R^(6X),—NR^(7X)S(═O)₂R^(8X), a silyl group, a nitro group, a cyano group, or ahalogen atom.

R^(1X) to R^(8X) represent a hydrogen atom, an aliphatic hydrocarbongroup, an aryl group, or a heteroaryl group.

The aliphatic hydrocarbon group, aryl group, and heteroaryl grouprepresented by R^(1X) to R^(8X) are the same as the aliphatichydrocarbon group, aryl group, and heteroaryl group represented by R¹¹to R¹⁴, and preferred forms thereof are also the same.

In particular, the compound represented by the formula (1) is preferablya compound represented by formula (8) below, more preferably a compoundrepresented by formula (10) below, and further preferably a compoundrepresented by formula (10′) below.

In the formula (8), R¹¹ to R¹⁴ respectively have the same meaning as R¹¹to R¹⁴ in the formula (1), and preferred forms thereof are also thesame. In the formula (8), preferably, R¹² and R¹⁴ represent an aliphatichydrocarbon group and R¹¹ and R¹³ represent an aryl group or aheteroaryl group. R⁸¹ to R⁸⁶ each independently represent a hydrogenatom or a substituent. The substituent represented by R⁸¹ to R⁸⁶ is thesame as the substituent represented by R¹⁵, and preferred forms thereofare also the same.

In the formula (10), X¹⁰¹ and X¹⁰² each independently represent anelectron-withdrawing group.

The term “electron-withdrawing group” refers to a group having apositive Hammett substituent constant. For the electron-withdrawinggroup, specifically, refer to Chem. Rev. 1BBl. 97, 165-195.

Examples of the electron-withdrawing group represented by X¹⁰¹ and X¹⁰²include a halogen atom, an acyl group, an arylcarbonyl group, analkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, ahalogenated alkyl group, a halogenated alkyloxy group, an aminocarbonylgroup, an alkanesulfonyl group, an arylsulfonyl group, a cyano group, anitro group, and a formyl group. In particular, the electron-withdrawinggroup is preferably a halogen atom, more preferably a fluorine atom or achlorine atom, and further preferably a chlorine atom.

n1 and n2 each independently represent an integer of 1 to 5. From theviewpoint of further improving yield, n1 and n2 preferably represent 3or less.

R¹² and R¹⁴ each independently represent an aliphatic hydrocarbon group.The aliphatic hydrocarbon group represented by R¹² and R¹⁴ is the sameas the aliphatic hydrocarbon group represented by R¹² and R¹⁴ in theformula (1), and preferred forms thereof are also the same. R⁸¹ to R⁸⁶respectively have the same meaning as R⁸¹ to R⁸⁶ in the formula (8).

In the formula (10′), X¹¹¹ to X¹¹⁶ each independently represent ahalogen atom. The halogen atom represented by X¹¹¹ to X¹¹⁶ is preferablya fluorine atom, a chlorine atom, a bromine atom, or an iodine atom andmore preferably a chlorine atom. R⁸¹ to R⁸⁶ respectively have the samemeaning as R⁸¹ to R⁸⁶ in the formula (8), and preferred forms thereofare also the same.

R¹² and R¹⁴ each independently represent an aliphatic hydrocarbon group.The aliphatic hydrocarbon group represented by R¹² and R¹⁴ has the samemeaning as the aliphatic hydrocarbon group represented by R¹² and R¹⁴ inthe formula (1), and preferred forms thereof are also the same.

Hereafter, the compound represented by the formula (1) will beexemplified, but is not limited thereto.

(1)-1 to (1)-52 in Table below show combinations of R¹¹, R¹², R¹³, andR¹⁴ shown in each basic skeleton below. That is, when the followingbasic skeleton is described as an example, it is intended that thecombination of R¹¹, R¹², R¹³, and R¹⁴ in the following basic skeletonmay be any of (1)-1 to (1)-52 in Table below.

R⁸¹ and R⁸² in each basic skeleton shown below each independentlyrepresent a substituent selected from the group consisting of a hydrogenatom, a cyano group, a fluorine atom, a chlorine atom, a bromine atom,an iodine atom, a trifluoromethyl group, a trifluoromethoxy group, atrichloromethyl group, a trichloromethoxy group, a phenyl group, a2-thiazolyl group, a 5-thiazolyl group, a 2-thienyl group, a 3-thienylgroup, a styryl group, a 2-thiazolylvinyl group, a 5-thiazolylvinylgroup, a 2-thienylvinyl group, a 3-thienylvinyl group, a phenylethynylgroup, a 2-thiazolylethynyl group, a 5-thiazolylethynyl group, a2-thienylethynyl group, a 3-thienylethynyl group, atrimethylsilylethynyl group, a triethylsilylethynyl group, atriisopropylethynyl group, and a 1-octynyl group. Herein, at least oneof R⁸¹ or R⁸² represents a group other than hydrogen.

In Table below, “Me” represents a methyl group, and “Et” represents anethyl group.

TABLE 1 No. R¹¹ R¹² R¹³ R¹⁴ (1)-1 2,4,6-trichlorophenyl Me2,4,6-trichlorophenyl Me (1)-2 phenyl Me phenyl Me (1)-3 4-nitrophenylMe 4-nitrophenyl Me (1)-4 4-methoxyphenyl Me 4-methoxyphenyl Me (1)-54-methylphenyl Me 4-methylphenyl Me (1)-6 4-chlorophenyl Me4-chlorophenyl Me (1)-7 3,4-dimethoxyphenyl Me 3,4-dimethoxyphenyl Me(1)-8 2-methoxyphenyl Me 2-methoxyphenyl Me (1)-9 4-tert-butylphenyl Me4-tert-butylphenyl Me (1)-10 2,4,5-trichlorophenyl Me2,4,5-trichlorophenyl Me (1)-11 perfluorophenyl Me perfluorophenyl Me(1)-12 2-chlorophenyl Me 2-chlorophenyl Me (1)-13 3-nitorophenyl Me3-nitorophenyl Me (1)-14 3-chlorophenyl Me 3-chlorophenyl Me (1)-152,5-dimethylphenyl Me 2,5-dimethylphenyl Me (1)-16 2-acetylphenyl Me2-acetylphenyl Me (1)-17 3,4-dimethylphenyl Me 3,4-dimethylphenyl Me(1)-18 2,4,6-trichlorophenyl Et 2,4,6-trichlorophenyl Et (1)-192,4,6-trichlorophenyl propyl 2,4,6-trichlorophenyl propyl (1)-202,4,6-trichlorophenyl isopropyl 2,4,6-trichlorophenyl Isopropyl (1)-212,4,6-trichlorophenyl butyl 2,4,6-trichlorophenyl butyl (1)-222,4,6-trichlorophenyl tert-butyl 2,4,6-trichlorophenyl tert-butyl (1)-232,4,6-trichlorophenyl benzyl 2,4,6-trichlorophenyl benzyl (1)-242,4,6-trichlorophenyl octyl 2,4,6-trichlorophenyl octyl (1)-252,4,6-trichlorophenyl allyl 2,4,6-trichlorophenyl allyl (1)-262,4,6-trichlorophenyl methoxyethyl 2,4,6-trichlorophenyl methoxyethyl(1)-27 2,4,6-trichlorophenyl ethoxyethyl 2,4,6-trichlorophenylEthoxyethyl (1)-28 2,4,6-trichlorophenyl 2-ethylhexyl2,4,6-trichlorophenyl 2-ethylhexyl (1)-29 2,4,6-trichlorophenyl isobutyl2,4,6-trichlorophenyl isobutyl (1)-30 2,4,6-trichlorophenyl hexyl2,4,6-trichlorophenyl hexyl (1)-31 2,4,6-trichlorophenyl cyclohexyl2,4,6-trichlorophenyl Cyclohexyl (1)-32 2,4,6-trichlorophenyl2-phenylethyl 2,4,6-trichlorophenyl 2-phenylethyl (1)-332,4,6-trichlorophenyl dodecyl 2,4,6-trichlorophenyl dodecyl (1)-342,4,6-trichlorophenyl 2,2,2-trifluoromethyl 2,4,6-trichlorophenyl2,2,2-trifluoromethyl (1)-35 2,4,6-trichlorophenyl2-(trimethylsilyl)ethyl 2,4,6-trichlorophenyl 2-(trimethylsilyl)ethyl(1)-36 2,4,6-trichlorophenyl pentyl 2,4,6-trichlorophenyl pentyl (1)-372,4,6-trichlorophenyl 2-bromoethyl 2,4,6-trichlorophenyl 2-bromoethyl(1)-38 2,4,6-trichlorophenyl isopentyl 2,4,6-trichlorophenyl Isopentyl(1)-39 2,4,6-trichlorophenyl 2-chloroethyl 2,4,6-trichlorophenyl2-chloroethyl (1)-40 2,4,6-trichlorophenyl Me 2,4,6-trichlorophenyl Me(1)-41 2,4,6-trichlorophenyl 2,4,6-trichlorophenyl Me Me (1)-42 Me Me2,4,6-trichlorophenyl 2,4,6-trichlorophenyl (1)-43 2,4,6-trichlorophenylMe 2,4,6-trichlorophenyl Me (1)-44 Me 2,4,6-trichlorophenyl Me2,4,6-trichlorophenyl (1)-45 2,4,6-trichlorophenyl 2,4,6-trichlorophenylMe Me (1)-46 2,4-dichlorophenyl Me 2,4-dichlorophenyl Me (1)-47 Me Me2,4-diichlorophenyl 2,4-diichlorophenyl (1)-48 2,6-dichlorophenyl Me2,6-dichlorophenyl Me (1)-49 2,4,6-trichlorophenyl cyclohexylethy2,4,6-trichlorophenyl cyclohexylethy (1)-50 2,4-dichlorophenyl2,4-dichlorophenyl Me Me (1)-51 2,4-dichlorophenyl Et 2,4-dichlorophenylEt (1)-52 2,4-dichlorophenyl propyl 2,4-dichlorophenyl propyl

Compound Represented by Formula (2)

In the formula (2), A¹¹ to A¹⁸ respectively have the same meaning as A¹¹to A¹⁸ in the formula (1), and preferred forms thereof are also thesame.

R³¹ and R⁵¹ each independently represent a substituent.

The substituent represented by R³¹ and R⁵¹ is not particularly limited,but is preferably a group selected from the above-described substituentgroup Z. Specifically, the substituent is preferably an alkyl group(preferably having 1 to 30 carbon atoms and more preferably having 4 to20 carbon atoms, and may be linear, chain-like, or cyclic), an alkenylgroup, an alkynyl group, an aryl group (preferably having 6 to 20 carbonatoms), or a heterocyclic group (including at least one of theabove-mentioned heteroatoms as a ring-constituting atom, preferablyhaving a 5-membered ring, a 6-membered ring, or a fused ring thereof,the number of ring-constituting carbon atoms is preferably 3 to 20),more preferably an alkyl group, an alkenyl group, an alkynyl group, anaryl group, or a heteroaryl group, further preferably an alkyl group, anaryl group, or a heteroaryl group, and particularly preferably an alkylgroup.

The above-mentioned alkyl group, alkenyl group, alkynyl group, arylgroup, heterocyclic group, and heteroaryl group may further have asubstituent. In the case of further having a substituent, thesubstituent is a group selected from the substituent group Z.

In particular, the substituent represented by R³¹ and R⁵¹ is preferablyan unsubstituted alkyl group, a halogenated alkyl group, an alkyl grouphaving an aryl group as a substituent, an alkyl group having aheterocyclic ring (preferably a heteroaryl group) as a substituent, anunsubstituted aryl group, an aryl group into which an alkyl group isintroduced, an unsubstituted heterocyclic group, a heterocyclic groupinto which an alkyl group is introduced, an alkyl group into which asilyl group is introduced, or an alkyl group into which one or morealkoxy groups are introduced. For the alkyl group having an aryl groupas a substituent and the alkyl group having a heterocyclic ring as asubstituent, the aryl group and the heterocyclic ring may further have asubstituent. In the case of further having a substituent, thesubstituent is a group selected from the substituent group Z, andpreferably a halogen atom.

The compound represented by the formula (2) is particularly preferably acompound represented by formula (9) below.

In the formula (9), R³¹ and R⁵¹ respectively have the same meaning asR³¹ and R⁵¹ in the formula (2), and preferred forms thereof are also thesame. R⁸¹ to R⁸⁶ respectively have the same meaning as R⁸¹ to R⁸⁶ in theformula (8), and preferred forms thereof are also the same.

Hereafter, examples of the compound represented by the formula (2) areshown, but the compound represented by the formula (2) is not limitedthereto.

No. R^(15A) R^(15B) R^(15C) R^(15D) R^(15E) R^(15G) R^(15H) R³¹ R⁵¹  1 HH H H H H H CH₃ CH₃  2 H H H H H H H nC₆H₁₃ nC₆H₁₃  3 H H H H H H H

 4 H H H H H H H CH₂C₃F₇ CH₂C₃F₇  5 H H H H H H H -isoPropyl -isoPropyl 6 H H H H H H H -tert-Butyl -tert-Butyl  7 H H H H H H H

 8 H H H H H H H C₂H₄C₅F₁₁ C₂H₄C₅F₁₁  9 Cl Cl Cl Cl Cl Cl Cl

10 F H H H F H H

11 F F F F F F F

12 CN H H H H H CN

13 Br H H H H H H

14 NO₂ H H H H H H

15 CH₃ nC₆H₁₃ H H H H H

16 CH₃ nC₆H₁₃ H H H H H

17 CO₂CH₃ H H H H H H

18 H -Ph H H H —Ph H

19 —COOH H H H H H H CF₃ C₂F₅ 20 H CF₃ H H H H H

21 OCH₃ H H H H H H

No. R^(15A) R^(15B) R^(15C) R^(15D) R^(15F) R^(15G) R^(15H) R³¹ R⁵¹ 22 HH H H H H H CH₃ CH₃ 23 H H H H H H H

nC₆H₁₃ 24 H H H H H H H

25

H H H H

H

CH₂C₃F₇ 26 H

H H

H H -isoPropyl -isoPropyl 27 H H H H H H H

No. R^(15A) R^(15B) R^(15D) R^(15E) R^(15F) R^(15H) R³¹ R⁵¹ 28 H H H H HH CH₃ CH₃ 29 H H H H H H nC₆H₁₃ nC₆H₁₃ 30 H H H H H H

31 H H H H H H CH₂C₃F₇ CH₂C₃F₇ 32 H H H H H H -isoPropyl -isoPropyl 33 HH H H H H -tert-Butyl -tert-Butyl 34 H H H H H H

35 H H H H H H C₂H₄C₅F₁₁ C₂H₄C₅F₁₁ 36 Cl Cl Cl Cl Cl Cl

37 H F H H F H

38 F F F F F F

39 H CN H H CN H

40 H H H H H Br

41 H H H H H NO₂

42 H H H H nC₆H₁₃ CH₃

43 H H H H H CO₂CH₃

44 —Ph H H H —Ph H

45 H H H H H —COOH CF₃ C₂F₅ 46 H H H H CF₃ H

47 H H H H H OCH₃

No. R^(15B) R^(15C) R^(15D) R^(15F) R^(15G) R^(15H) R³¹ R⁵¹ 48 H H H H HH CH₃ CH₃ 49 H H H H H H nC₆H₁₃ nC₆H₁₃ 50 H H H H H H

51 H H H H H H CH₂C₃F₇ CH₂C₃F₇ 52 H H H H H H -isoPropyl -isoPropyl 53 HH H H H H -tert-Butyl -tert-Butyl 54 H H H H H H

55 H H H H H H C₂H₄C₅F₁₁ C₂H₄C₅F₁₁ 56 Cl Cl Cl Cl Cl Cl

57 F H H H F H

58 F F F F F F

59 CN H H H CN H

60 Br H H H H H

61 NO₂ H H H H H

62 CH₃ nC₆H₁₃ H H H H

63 CO₂CH₃ H H H H H

64 H Ph H H H Ph

65 —COOH H H H H H CF₃ C₂F₅ 66 H CF₃ H H H H

67 OCH₃ H H H H H

No. R^(15A) R^(15C) R^(15D) R^(15F) R^(15G) R^(15H) R³¹ R⁵¹ 68 H H H H HH CH₃ CH₃ 69 H H H H H H

nC₆H₁₃ 70 H H H H H H

71

H H H H

CH₂C₃F₇ 72 H

H H

H -isoPropyl -isoPropyl 73 H H H H H H

No. R^(15A) R^(15B) R^(15D) R^(15F) R^(15G) R^(15H) R³¹ R⁵¹ 74 H H H H HH CH₃ CH₃ 75 H H H H H H

nC₆H₁₃ 76 H H H H H H

77

H H H H

CH₂C₃F₇ 78 H

H H

H -isoPropyl -isoPropyl 79 H H H H H H

No. R^(15A) R^(15B) R^(15E) R^(15F) R^(15G) R^(15H) R³¹ R⁵¹ 80 H H H H HH CH₃ CH₃ 81 Cl H H H H H nC₆H₁₃ nC₆H₁₃ 82 F H H H H H

83 H H H H H

CH₂C₃F₇ CH₂C₃F₇ 84 H

H H

H -isoPropyl -isoPropyl 85 H H H H H H -tert-Butyl -tert-Butyl 86 H H HH H H

87 H H H H H H C₂H₄C₅F₁₁ C₂H₄C₅F₁₁ 88 Cl H Cl H H H

89 F H F H H H

90 F F F F F F

91 CN H H H H H

92 Br H H H H Br

93 NO₂ H H H H H

94 CH₃ H H H H H

95 CO₂CH₃ H H H H H

96 H H H H H H

97 —COOH H H H H H CF₃ C₂F₅ 98 H H H H H H

99 OCH₃ H H H H H

No. R^(15A) R^(15D) R^(15E) R^(15F) R^(15G) R^(15H) R³¹ R⁵¹ 100 CN H H HH H CH₃ CH₃ 101 Br H H H H Br nC₆H₁₃ nC₆H₁₃ 102 NO₂ H H H H H

103 —COOH H H H H H

104 H H H H H H

105 OCH₃ H H H H H

No. R^(15B) R^(15F) R³¹ R⁵¹ 106 H H

107 H H CF₃ CF₃ 108 H H nC₈H₁₇ nC₈H₁₇ 109 H H nC₁₀H₂₁ nC₁₀H₂₁ 110 H H

111 H H

112 H H

113 H H

114 H H

115 H H

116 H H

117 H H

118 H H

119 H H

120 H H

121 H H

122 H H

123 H H

124 H H

125 H H

126 H H

127 H H

128 H H

129 H H

130 H H

131 Br Br

132 CN CN

133

134

135

136 CN CN *—C₈H₁₇ *—C₈H₁₇ 137 F F

138 H H

139 H H *—CH₂CH₂C₆F₁₃

140 H H

141 H H

142 H H

143 H H

144 H H

145 H H

146 H H

147 H H

148 F F *—CH₂CH₂C₆F₁₃

149 CN CN *—CH₂CH₂C₆F₁₃

150 Cl Cl *—C₈H₁₇ *—C₈H₁₇ 151 CN CN

152 F F

153 Cl Cl

154 H H *—C₂H₅ *—C₂H₅ 155 H H *—C₃H₇ *—C₃H₇ 156 H H *—C₄H₉ *—C₄H₉ 157 HH *—C₅H₁₁ *—C₅H₁₁ 158 H H *—C₆H₁₃ *—C₆H₁₃ 159 H H *—C₇H₁₅ *—C₇H₁₅ 160

*—C₈H₁₇ *—C₈H₁₇ 161

*—C₈H₁₇ *—C₈H₁₇ 162 *—C≡CSiMe₃ *—C≡CSiMe₃ *—C₈H₁₇ *—C₈H₁₇ 163 *—C≡CC₆H₁₃*—C≡CC₆H₁₃ *—Me *—Me 164 F F *—C₈H₁₇ *—C₈H₁₇ 165 Br Br *—C₈H₁₇ *—C₈H₁₇166 H H *—C₅H₁₁

167 H H

168 H H

169 H H

170 H H

171 CN CN

172 H H

173 H H

174 H H

175 H H

176

H H 177 *—C≡CC₆H₁₃ *—C≡CC₆H₁₃ H H 178 *—C₈H₁₇ *—C₈H₁₇ H H 179 H H

180 H H

181 CN CN

182 CN CN

183 CN CN

184 CN CN

185 CN CN

186 H H

187 H H

188

*—C₈H₁₇ *—C₈H₁₇ 189

*—C₈H₁₇ *—C₈H₁₇ 190

*—C₈H₁₇ *—C₈H₁₇ 191

*—C₈H₁₇ *—C₈H₁₇ 192

*—C₈H₁₇ *—C₈H₁₇ 193

*—C₈H₁₇ *—C₈H₁₇ 194

*—C₈H₁₇ *—C₈H₁₇ 195

*—C₈H₁₇ *—C₈H₁₇ 196 H H *—C₅H₁₁

197 F F *—C₅H₁₁

198 CN CN *—C₅H₁₁

199 CN CN

*—C₈H₁₇ 200 F F

201 F F

202 F F

203 CN CN

204 F F

205 CN CN

206 F F

207 CN CN

208 F F

209 CCl₃ CCl₃ *—C₈H₁₇ *—C₈H₁₇ 210 H H *—C₂H₅

211 H H *—C₃H₇

212 H H *—C₄H₉

213 H H *—C₆H₁₃

214 H H *—C₇H₁₅

215 H H *—C₈H₁₇

216 H H *—C₁₀H₂₁

217 H H *—C₁₂H₂₅

218 H H

219 H H

220 H H

221 F F

222 F F

223 F F

223 CN CN

223 CN CN

223 CN CN

224 F F

225 F F

226 F F

227 CN CN

228 CN CN

229 CN CN

230 H H

231 CN CN

232 F F

Amine Compound

In the production method according to an embodiment of the presentinvention, an amine compound to be reacted with the compound representedby the formula (1) is not particularly limited, but is preferably aprimary amine or a protected primary amine.

The primary amine is not particularly limited, and is, for example, anamine compound represented by formula (Y1) below.

R^(Y1)—NH₂  Formula (Y1)

In the formula (Y1), R^(Y1) represents a substituent.

The substituent represented by R^(Y1) is not particularly limited, butis preferably a group selected from the above-described substituentgroup Z. Specifically, the substituent is preferably an alkyl group (thenumber of carbon atoms is preferably 1 to 20, from the viewpoint ofcarrier mobility in the case of being used as an organic semiconductorcompound, the lower limit of the number of carbon atoms is morepreferably 4 or more, and the upper limit of the number of carbon atomsis more preferably 15 or less and further preferably 8 or less, and maybe linear, chain-like, or cyclic), an alkenyl group, an alkynyl group,an aryl group (preferably having 6 to 20 carbon atoms), or aheterocyclic group (including at least one of the above-mentionedheteroatoms as a ring-constituting atom, preferably having a 5-memberedring, a 6-membered ring, or a fused ring thereof, the number ofring-constituting carbon atoms is preferably 3 to 20), more preferablyan alkyl group, an alkenyl group, an alkynyl group, an aryl group, or aheteroaryl group, further preferably an alkyl group, an aryl group, or aheteroaryl group, and particularly preferably an alkyl group.

The above-mentioned alkyl group, alkenyl group, alkynyl group, arylgroup, heterocyclic group, and heteroaryl group may further have asubstituent. In the case of further having a substituent, thesubstituent is a group selected from the substituent group Z.

In particular, the substituent represented by R^(Y1) is more preferablyan unsubstituted alkyl group, a halogenated alkyl group, an alkyl grouphaving an aryl group as a substituent, an alkyl group having aheterocyclic ring (preferably a heteroaryl group) as a substituent, anunsubstituted aryl group, an aryl group into which an alkyl group isintroduced, an unsubstituted heterocyclic group, a heterocyclic groupinto which an alkyl group is introduced, an alkyl group into which asilyl group is introduced, or an alkyl group into which one or morealkoxy groups are introduced. For the alkyl group having an aryl groupas a substituent and the alkyl group having a heterocyclic ring as asubstituent, the aryl group and the heterocyclic ring may further have asubstituent. In the case of further having a substituent, thesubstituent is a group selected from the substituent group Z, andpreferably a halogen atom.

Specific examples of the amine compound represented by the formula (Y1)include methylamine, ethylamine, 2-trimethylsilylethylamine,propylamine, isopropylamine, cyclopropylamine, butylamine,isobutylamine, tert-butylamine, sec-butylamine, cyclobutylamine,3-methylbutylamine, pentylamine, neopentylamine, 2-methylbutylamine,cyclopentylamine, hexylamine, cyclohexylamine, 1-methylpentylamine,heptylamine, octylamine, 2-ethylhexylamine, 1-methyloctylamine,decylamine, dodecylamine, benzylamine, phenylethylamine,phenylpropylamine, phenylbutylamine, cyclohexylethylamine,2-thienylethylamine, 2-thiazolylethylamine, 5-thiazolylethylamine,2-(trimethylsilyl)ethylamine, butoxypropylamine, methoxybutylamine,methylpentylamine, aniline, p-octylaniline, p-octylphenylethylamine,p-ethylphenylethylamine, p-hexylphenylethylamine,p-decylphenylethylamine, 3,7-dimethyloctylamine,perfluorophenylethylamine, 2-thienylethylamine, 2-thiazolylethylamine,5-thiazolylethylamine, 2-hexyldecylamine, 2-octyldodecylamine,1H,1H-heptafluorobutylamine, 1H,1H-undecafluorobutylamine,1H,1H,2H,2H-tridecafluorooctylamine, p-fluorophenylamine,2-(4-pyridyl)ethylamine, 2,4-dimethoxymethylamine,2-(3-pyridyl)ethylamine, toluidine, butoxypropylamine, and3,6,9,12-tetraoxadecaneamine.

The protected primary amine is intended to be a compound having astructure in which one of hydrogen atoms bonded to the nitrogen atom inthe formula (Y1) is protected with a protecting group. Specifically, theprotected primary amine is a primary amine compound that can be used inthe production method of the second embodiment described later and thatis represented by formula (3).

The protected primary amine will be described later in the productionmethod of the second embodiment.

Method for Producing Cyclic Imide Compound

The production method according to an embodiment of the presentinvention includes a step of reacting the compound represented by theformula (1) with at least one amine compound to obtain the compoundrepresented by the formula (2).

Hereafter, the case where substituents represented by R³¹ and R⁵¹ in theformula (2) are the same will be described as a first embodiment, andthe case where substituents represented by R³¹ and R⁵¹ in the formula(2) are not the same will be described as a second embodiment.

Production Method in First Embodiment

The production method in the first embodiment includes a step X below.

Step X: a step of heating a composition including a compound representedby formula (1) and at least one amine compound to obtain a compoundrepresented by formula (2)

The compound represented by the formula (1), the compound represented bythe formula (2), and the amine compound are as described above.

Through the step X, amidation/imidation reactions between two adjacentester groups in the compound represented by the formula (1) and an aminecompound (specifically, an amidation/imidation reaction between —COOR¹¹and —COOR¹⁴ and an amine compound, and an amidation/imidation reactionbetween —COOR¹² and —COOR¹³ and an amine compound) are caused to form acyclic imide compound represented by formula (2).

The amine compound may be either a primary amine or a protected primaryamine, but is preferably a primary amine from the viewpoint that adeprotection step of obtaining an intended cyclic imide compoundrepresented by the formula (2) is not necessary.

The amount of the amine compound used is preferably 2.0 to 10 molarequivalents and more preferably 2.0 to 6.0 molar equivalents relative to1 molar equivalent of the compound represented by the formula (1).

The composition may include a solvent.

A single solvent may be used, or two or more solvents may be used in amixed manner.

Non-limiting examples of the solvent include hydrocarbon solvents, ethersolvents, amide solvents, alcohol solvents, nitrile-based solvents, andsulfoxide solvents.

Examples of the hydrocarbon solvent include pentane, hexane, heptane,octane, decane, toluene, ethylbenzene, xylene, diethylbenzene,fluorobenzene, trifluoromethylbenzene, chloroform, dichloromethane,1,1,2,2-tetrachloroethane, 1,1,2-trichloroethane, chlorobenzene,dichlorobenzene, trichlorobenzene, mesitylene, amylbenzene, decalin,1-methylnaphthalene, 1-ethylnaphthalene, 1-chloronaphthalene,1-fluoronaphthalene, 1,6-dimethylnaphthalene, nitrobenzene, andtetralin.

Examples of the ether solvent include anisole, diethyl ether, dibutylether, diisopropyl ether, cyclopentyl methyl ether, diphenyl ether,tetrahydropyran, dioxane, dimethoxyethane, diethoxyethane, andtetrahydrofuran.

Examples of the amide solvent include N,N-dimethylformamide,N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolidinone,and N,N-dimethylacetamide.

Examples of the alcohol solvent include methanol, ethanol, propanol,isopropanol, amyl alcohol, benzyl alcohol, ethylene glycol, diethyleneglycol, propylene glycol, and glycerol.

Examples of the nitrile-based solvent include acetonitrile andbenzonitrile.

Examples of the sulfoxide solvent include dimethyl sulfoxide andsulfolane.

In particular, the solvent is preferably a solvent having a boilingpoint of 70° C. or higher and more preferably a solvent having a boilingpoint of 90° C. or higher.

Examples of the solvent having a boiling point of 90° C. or higherinclude heptane, octane, decane, toluene, ethylbenzene, xylene,diethylbenzene, fluorobenzene, trifluoromethylbenzene, chlorobenzene,dichlorobenzene, trichlorobenzene, mesitylene, amylbenzene, decalin,1-methylnaphthalene, 1-ethylnaphthalene, 1-chloronaphthalene,1-fluoronaphthalene, 1,6-dimethylnaphthalene, nitrobenzene,1,1,2,2-tetrachloroethane, 1,1,2-trichloroethane, benzonitrile,tetralin, anisole, dibutyl ether, cyclopentyl methyl ether, diphenylether, dioxane, diethoxyethane, N,N-dimethylformamide,N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolidinone,N,N-dimethylacetamide, 1-propanol, 1-butanol, isobutyl alcohol,2-butanol, amyl alcohol, benzyl alcohol, ethylene glycol, diethyleneglycol, propylene glycol, glycerol, dimethyl sulfoxide, and sulfolane.

When the composition includes a solvent, the content of the solvents ispreferably 75.0 to 99.9 mass % and more preferably 80.0 to 98.0 mass %relative to the total mass of the composition.

The reaction temperature is not particularly limited, but is preferably20° C. to 250° C. and more preferably 50° C. to 200° C.

The reaction time varies depending on the solvent used and the reactionconditions including a reaction temperature, but is normally 1 to 24hours and preferably 1 to 20 hours.

After completion of the heating reaction, if necessary, the obtainedcompound represented by the formula (2) may be purified by separationand purification means including washing, extraction, drying,filtration, concentration, recrystallization, reprecipitation,crystallization, centrifugation, adsorption, column purification, and/orsublimation purification, and is preferably purified by separation andpurification means including sublimation purification.

As described above, the compound represented by the formula (1) ispreferably the compound represented by the formula (8), and the compoundrepresented by the formula (2) is preferably the compound represented bythe formula (9).

Hereafter, a preferred embodiment (hereafter, also referred to as “firstembodiment-1”) of the method for producing the compound represented bythe formula (9) (the formula (9′) shown later corresponds to a compoundin which R³¹ and R⁵¹ represent the same substituent in the formula (9))from the compound represented by the formula (8) (the formula (11A)shown later corresponds to the formula (8)).

Preferred Embodiment of Method for Producing Compound Represented byFormula (9) (First Embodiment-1)

The production method according to the first embodiment-1 includes astep X′ below.

Step X′: a step of reacting a compound represented by formula (X1) belowwith a compound represented by formula (X2) below to obtain acomposition including a compound represented by formula (11A) below anda compound represented by formula (11B) below, and then reacting thecomposition with a first amine compound represented by formula (14)below without subjecting the composition to column purification toobtain a compound represented by formula (9′) below

The compound represented by the formula (9′) below is a compound coveredby the above-described compound represented by the formula (9).Specifically, the compound represented by the formula (9′) belowcorresponds to a compound in which the substituents represented by R³¹and R⁵¹ in the compound represented by the formula (9) are the same. Thecompound represented by the formula (11A) corresponds to the compoundrepresented by the formula (8).

The production method according to the first embodiment-1 preferablyfurther includes a step Y0′ below.

Step Y0′: a step of further purifying the compound represented by theformula (X2) before reacting the compound represented by the formula(X1) with the compound represented by the formula (X2)

The compounds represented by the formula (X1), the formula (X2), theformula (11A), and the formula (11B) in the step X′ are the same ascompounds represented by formula (X1), formula (X2), formula (11A), andformula (11B) in step Y1′ described later, and preferred forms thereofare also the same.

The compounds represented by the formula (X1), the formula (X2), theformula (11A), and the formula (11B) will be described later in theproduction method according to the second embodiment.

The first amine compound represented by the formula (14) in the step Xis the same as a second amine compound represented by formula (14) instep Y1′ described later, and preferred forms thereof are also the same.

The first amine compound represented by the formula (14) will bedescribed later in the production method of the second embodiment.

In the step X′, the procedure for reacting the compound represented bythe formula (X1) with the compound represented by the formula (X2) toobtain the composition including the compound represented by the formula(11A) and the compound represented by the formula (11B) is the same asthat in the step Y1′ described later, and preferred forms thereof arealso the same.

The above procedure will be described later in the production method ofthe second embodiment.

In the step X′, the compound represented by the formula (11B) is aby-product formed in a synthesis reaction of reacting the compoundrepresented by the formula (X1) with the compound represented by theformula (X2) to obtain the compound represented by the formula (11A).The formation of the compound represented by the formula (11B) as aby-product is probably caused by formic acid that may be included as animpurity in the compound represented by the formula (X2) (the compoundrepresented by the formula (X2) is, for example, 2,4,6-trichlorophenylformate). In the step X′, the formation of the compound represented bythe formula (11B) as a by-product can be suppressed by performing thestep (step Y0′) of purifying the compound represented by the formula(X2) before the reaction of the compound represented by the formula (X1)with the compound represented by the formula (X2).

The step Y0′ that may be included in the production method according tothe first embodiment-1 is the same as the step Y0′ that may be includedin the production method according to the second embodiment-1 describedlater, and preferred forms are also the same.

The procedure of the step Y0′ will be described later in the productionmethod according to the second embodiment.

In the step X′, a step of reacting a composition obtained through acoupling reaction of the compound represented by the formula (X1) andthe compound represented by the formula (X2) with the first aminecompound represented by the formula (14) without column purification isperformed. From the viewpoint of further improving the purity of thecompound represented by the formula (9′), which is a target compound,the composition includes at least the compound represented by theformula (11A), and the content of the compound represented by theformula (11B) is preferably 3.0 mass % or less and more preferably 1.0mass % or less relative to the total solid content of the composition.When the step Y0′ is performed, the content of the compound representedby the formula (11B) in the composition of the step X′ can be adjustedto 3.0 mass % or less relative to the total solid content of thecomposition.

The lower limit of the content of the compound represented by theformula (11B) is usually 0 mass % or more and often 0.01 mass % or morerelative to the total solid content of the composition.

The term “solid content” refers to components in a composition fromwhich solvents are removed. Even if components other than solvents inthe composition are liquid, the components are regarded as solidcontents.

If necessary, the composition may be purified by separation andpurification means other than column purification (such as washing,extraction, drying, filtration, concentration, recrystallization,reprecipitation, crystallization, adsorption, and centrifugation) aftercompletion of the coupling reaction.

Specifically, the step of reacting the composition with the first aminecompound represented by the formula (14) is preferably a step of addingthe first amine compound represented by the formula (14) to thecomposition and heating the mixture to obtain the compound representedby the formula (9′).

The specific procedure is the same as that of the step X of theproduction method in the first embodiment described above, and thepreferred form is also the same.

Second Embodiment

The production method according to the second embodiment includes stepsY1 to Y4 below.

Step Y1: a step of reacting the compound represented by the formula (1)with a first amine compound represented by formula (3) below to obtain acompound represented by formula (4) below

Step Y2: a step of reacting the compound represented by the formula (4)with a second amine compound represented by formula (5) below to obtaina compound represented by formula (6) below

Step Y3: a step of removing P³¹ serving as a protecting group from thecompound represented by the formula (6) to obtain a compound representedby formula (7) below

Step Y4: a step of obtaining a compound represented by the formula (2)from the compound represented by the formula (7)

By the production method according to the second embodiment, a compound(2) having different substituents represented by R³¹ and R⁵¹ can beproduced with high purity.

Hereafter, first, the compounds represented by the formulae (3) to (7)will be described, and then the steps Y1 to Y4 will be described.

Compounds Represented by Formulae (3) to (7)

In the formula (3), R³¹ represents a substituent. P³¹ represents aprotecting group.

In the formula (3), the substituent represented by R³¹ is the same asthe substituent represented by R³¹ and R⁵¹ in the formula (2).

The substituent represented by R³¹ of the first amine compoundrepresented by the formula (3) can be exemplified by the samesubstituents as those represented by R^(Y1) of the amine compoundrepresented by (Y1), and preferred forms thereof are also the same.

Non-limiting examples of the protecting group represented by P³¹ includea (hetero)arylmethyl group (the (hetero)arylmethyl group refers to anarylmethyl group and a heteroarylmethyl group, which are specifically abenzyl group, a naphthylmethyl group, a 2-methoxybenzyl group, ap-methoxybenzyl group, a 2,4-dimethoxybenzyl group, a3,4,5-trimethoxybenzyl group, a 3,4-dimethoxybenzyl group, a2-thienylmethyl group, and a 2-furylmethyl group), anitrobenzenesulfonyl group, a dinitrobenzenesulfonyl group, atert-butoxycarbonyl group, an allyloxycarbonyl group, abenzyloxycarbonyl group, a methoxycarbonyl group, a2,2,2-trichloroethoxycarbonyl group, a 9-fluorenylmethoxycarbonyl group,a trimethylsilylethoxycarbonyl group, and a(2-trimethylsilyl)ethanesulfonyl group. The (hetero)arylmethyl group ispreferable.

The first amine compound represented by the formula (3) corresponds tothe above-described protected primary amine.

In the formula (4), A¹¹ to A¹⁸ and R¹² to R¹⁴ respectively have the samemeaning as A¹¹ to A¹⁸ and R¹² to R¹⁴ in the formula (1), and preferredforms thereof are also the same. R³¹ and P³¹ respectively have the samemeaning as R³¹ and P³¹ in the formula (3), and preferred forms thereofare also the same.

In the formula (5), the substituent represented by R⁵¹ is the same asthat represented by R⁵¹ in the formula (2), and preferred forms thereofare also the same.

The second amine compound represented by the formula (5) is the same asthe primary amine represented by the formula (Y1), and preferred formsthereof are also the same.

In the formula (6), A¹¹ to A¹⁸ and R¹⁴ respectively have the samemeaning as A¹¹ to A¹⁸ and R¹⁴ in the formula (1), and preferred formsthereof are also the same. R³¹ and P³¹ respectively have the samemeaning as R³¹ and P³¹ in the formula (3), and preferred forms thereofare also the same. R⁵¹ has the same meaning as R⁵¹ in the formula (5),and preferred forms thereof are also the same.

In the formula (7), A¹¹ to A¹⁸ and R¹⁴ respectively have the samemeaning as A¹¹ to A¹⁸ and R¹⁴ in the formula (1), and preferred formsthereof are also the same. R³¹ has the same meaning as R³¹ in theformula (3), and preferred forms thereof are also the same. R⁵¹ has thesame meaning as R⁵¹ in the formula (5), and preferred forms thereof arealso the same.

Hereafter, the compound represented by the formula (4), the compoundrepresented by the formula (6), and the compound represented by theformula (7) are individually exemplified.

Formula (4)

Examples of the compound represented by the formula (4) are shown below,but the compound represented by the formula (4) is not limited thereto.

(4)-1 to (4)-71 in Table below show combinations of R¹¹, R¹², R¹³, R¹⁴,R³¹, and P³¹ shown in each basic skeleton below. In Table below, “Me”represents a methyl group, and “Et” represents an ethyl group.

R⁸¹ and R⁸² in the basic skeletons shown below each independentlyrepresent a substituent selected from the group consisting of a hydrogenatom, a cyano group, a fluorine atom, a chlorine atom, a bromine atom,an iodine atom, a trifluoromethyl group, a trifluoromethoxy group, atrichloromethyl group, a trichloromethoxy group, a 2-thiazolyl group, a5-thiazolyl group, a 2-thienyl group, a 3-thienyl group, a styryl group,a 2-thiazolylvinyl group, a 5-thiazolylvinyl group, a 2-thienylvinylgroup, a 3-thienylvinyl group, a phenylethynyl group, a2-thiazolylethynyl group, a 5-thiazolylethynyl group, a 2-thienylethynylgroup, a 3-thienylethynyl group, a trimethylsilylethynyl group, atriethylsilylethynyl group, a triisopropylethynyl group, and a 1-octynylgroup. Herein, at least one of R⁸¹ or R⁸² represents a group other thanhydrogen.

TABLE 2 No.

(4)-1 Me 2,4,6-trichlorophenyl Me 2-phenylethyl p-methoxybenzyl (4)-2 Me2,4,6-trichlorophenyl Me 2-phenylethyl 2-nitrobenzenesulfonyl (4)-3 Me2,4,6-trichlorophenyl Me 2-phenylethyl 2-nitrobenzenesulfonyl (4)-4 Me2,4,6-trichlorophenyl Me 2-phenylethyl 2,4-dinitrobenzeneslufonyl (4)-5Me 2,4,6-trichlorophenyl Me 2-phenylethyl tert-butoxycarbonyl (4)-6 Me2,4,6-trichlorophenyl Me 2-phenylethyl allyloxycarbonyl (4)-7 Me2,4,6-trichlorophenyl Me 2-phenylethyl Benzyloxycarbonyl (4)-8 Me2,4,6-trichlorophenyl Me 2-phenylethyl methoxycarbonyl (4)-9 Me2,4,6-trichlorophenyl Me 2-phenylethyl Trichloromethylcarbonyl (4)-10 Me2,4,6-trichlorophenyl Me 2-phenylethyl 9-fluorenylmethyloxycarbonyl(4)-11 Me 2,4,6-trichlorophenyl Me 2-phenylethyl2-(trimethylsilyl)ethoxycarbonyl (4)-12 Me 2,4,6-trichlorophenyl Mepentyl p-methoxybenzyl (4)-13 Me 2,4,6-trichlorophenyl Me octylp-methoxybenzyl (4)-14 Me 2,4,6-trichlorophenyl Me 2-cyclohexylethylp-methoxybenzyl (4)-15 Me 2,4,6-trichlorophenyl Me 2-(2-thienyl)ethylp-methoxybenzyl (4)-16 Me 2,4,6-trichlorophenyl Me 1-methylpentylp-methoxybenzyl (4)-17 Me phenyl Me 2-phenylethyl p-methoxybenzyl (4)-18Me 4-nitrophenyl Me 2-phenylethyl p-methoxybenzyl (4)-19 Me4-methoxyphenyl Me 2-phenylethyl p-methoxybenzyl (4)-20 Me4-methylphenyl Me 2-phenylethyl p-methoxybenzyl (4)-21 Me 4-chlorophenylMe 2-phenylethyl p-methoxybenzyl (4)-22 Me 3,4-dimethoxyphenyl Me2-phenylethyl p-methoxybenzyl (4)-23 Me 2-methoxyphenyl Me 2-phenylethylp-methoxybenzyl (4)-24 Me 4-tert-butylphenyl Me 2-phenylethylp-methoxybenzyl (4)-25 Me 2,4,5-trichlorophenyl Me 2-phenylethylp-methoxybenzyl (4)-26 Me perfluorophenyl Me 2-phenylethylp-methoxybenzyl (4)-27 Me 2-chlorophenyl Me 2-phenylethylp-methoxybenzyl (4)-28 Me 3-nitorophenyl Me 2-phenylethylp-methoxybenzyl (4)-29 Me 3-chlorophenyl Me 2-phenylethylp-methoxybenzyl (4)-30 Me 2,5-dimethylphenyl Me 2-phenylethylp-methoxybenzyl (4)-31 Me 2-acetylphenyl Me 2-phenylethylp-methoxybenzyl (4)-32 Me 3,4-dimethylphenyl Me 2-phenylethylp-methoxybenzyl (4)-33 Et 2,4,6-trichlorophenyl Et 2-phenylethylp-methoxybenzyl (4)-34 Propyl 2,4,6-trichlorophenyl Propyl 2-phenylethylp-methoxybenzyl (4)-35 isopropyl 2,4,6-trichlorophenyl Isopropyl2-phenylethyl p-methoxybenzyl (4)-36 butyl 2,4,6-trichlorophenyl butyl2-phenylethyl p-methoxybenzyl (4)-37 tert-butyl 2,4,6-trichlorophenyltert-butyl 2-phenylethyl p-methoxybenzyl (4)-38 benzyl2,4,6-trichlorophenyl benzyl 2-phenylethyl p-methoxybenzyl (4)-39 octyl2,4,6-trichlorophenyl octyl 2-phenylethyl p-methoxybenzyl (4)-40 allyl2,4,6-trichlorophenyl allyl 2-phenylethyl p-methoxybenzyl (4)-41methoxyethyl 2,4,6-trichlorophenyl methoxyethyl 2-phenylethylp-methoxybenzyl (4)-42 ethoxyethyl 2,4,6-trichlorophenyl Ethoxyethyl2-phenylethyl p-methoxybenzyl (4)-43 2-ethylhexyl 2,4,6-trichlorophenyl2-ethylhexyl 2-phenylethyl p-methoxybenzyl (4)-44 isobutyl2,4,6-trichlorophenyl isobutyl 2-phenylethyl p-methoxybenzyl (4)-45hexyl 2,4,6-trichlorophenyl hexyl 2-phenylethyl p-methoxybenzyl (4)-46cyclohexyl 2,4,6-trichlorophenyl Cyclohexyl 2-phenylethylp-methoxybenzyl (4)-47 2-phenylethyl 2,4,6-trichlorophenyl 2-phenylethyl2-phenylethyl p-methoxybenzyl (4)-48 dodecyl 2,4,6-trichlorophenyldodecyl 2-phenylethyl p-methoxybenzyl (4)-49 2,2,2-trifluoromethyl2,4,6-trichlorophenyl 2,2,2-trifluoromethyl 2-phenylethylp-methoxybenzyl (4)-50 2-(trimethylsilyl)ethyl 2,4,6-trichlorophenyl2-(trimethylsilyl)ethyl 2-phenylethyl p-methoxybenzyl (4)-51 pentyl2,4,6-trichlorophenyl pentyl 2-phenylethyl p-methoxybenzyl (4)-522-bromoethyl 2,4,6-trichlorophenyl 2-bromoethyl 2-phenylethylp-methoxybenzyl (4)-53 isopentyl 2,4,6-trichlorophenyl Isopentyl2-phenylethyl p-methoxybenzyl (4)-54 2-chloroethyl 2,4,6-trichlorophenyl2-chloroethyl 2-phenylethyl p-methoxybenzyl (4)-55 Me2,4,6-trichlorophenyl Me 2-phenylethyl p-methoxybenzyl (4)-562,4,6-trichlorophenyl Me Me 2-phenylethyl p-methoxybenzyl (4)-572,4,6-trichlorophenyl Me Me 2-phenylethyl p-methoxybenzyl (4)-58 Me2,4,6-trichlorophenyl Me 2-phenylethyl p-methoxybenzyl (4)-59 Me2,4,6-trichlorophenyl Me 2-phenylethyl p-methoxybenzyl (4)-602,4,6-trichlorophenyl Me Me 2-phenylethyl p-methoxybenzyl (4)-61 Me2,4,6-trichlorophenyl Me 2-phenylethyl p-methoxybenzyl (4)-62 Me2,4,6-trichlorophenyl 2,4,6-trichlorophenyl 2-phenylethylp-methoxybenzyl (4)-63 Me 2,4,6-trichlorophenyl Me 2-phenylethylp-methoxybenzyl (4)-64 Me 2,4,6-trichlorophenyl Me 2-phenylethylp-methoxybenzyl (4)-65 2,4,6-trichlorophenyl Me Me 2-phenylethylp-methoxybenzyl (4)-66 Me 2,4,6-trichlorophenyl Me 2-phenylethylp-methoxybenzyl (4)-67 Me 2,4,6-trichlorophenyl Me 2-phenylethyl benzyl(4)-68 Me 2,4,6-trichlorophenyl Me 2-phenylethyl 2-methoxybenzyl (4)-69Me 2,4,6-trichlorophenyl Me 2-phenylethyl 2,4-dimethoxybenzyl (4)-70 Me2,4,6-trichlorophenyl Me 2-phenylethyl 3,4,5-trimethoxybenzyl (4)-71 Me2,4,6-trichlorophenyl Me 2-phenylethyl 3,4-dimethoxybenzyl

indicates data missing or illegible when filed

Formula (6)

Examples of the compound represented by the formula (6) are shown below,but the compound represented by the formula (6) is not limited thereto.

(6)-1 to (6)-59 in Table below show combinations of R¹¹, R¹⁴, R³¹, R⁵¹,and P³¹ shown in each basic skeleton below. In Table below, “Me”represents a methyl group, and “Et” represents an ethyl group.

R⁸¹ and R⁸² in the basic skeletons shown below each independentlyrepresent a substituent selected from the group consisting of a hydrogenatom, a cyano group, a fluorine atom, a chlorine atom, a bromine atom,an iodine atom, a trifluoromethyl group, a trifluoromethoxy group, atrichloromethyl group, a trichloromethoxy group, a 2-thiazolyl group, a5-thiazolyl group, a 2-thienyl group, a 3-thienyl group, a styryl group,a 2-thiazolylvinyl group, a 5-thiazolylvinyl group, a 2-thienylvinylgroup, a 3-thienylvinyl group, a phenylethynyl group, a2-thiazolylethynyl group, a 5-thiazolylethynyl group, a 2-thienylethynylgroup, a 3-thienylethynyl group, a trimethylsilylethynyl group, atriethylsilylethynyl group, a triisopropylethynyl group, and a 1-octynylgroup. Herein, at least one of R⁸¹ or R⁸² represents a group other thanhydrogen.

TABLE 3 No.

(6)-1 Me pentyl 2-phenylethyl p-methoxybenzyl (6)-2 Me pentyl2-phenylethyl 2-nitrobenzenesulfonyl (6)-3 Me pentyl 2-phenylethyl2-nitrobenzenesulfonyl (6)-4 Me pentyl 2-phenylethyl2,4-dinitrobenzeneslufonyl (6)-5 Me pentyl 2-phenylethyltert-butoxycarbonyl (6)-6 Me pentyl 2-phenylethyl allyloxycarbonyl (6)-7Me pentyl 2-phenylethyl Benzyloxycarbonyl (6)-8 Me pentyl 2-phenylethylmethoxycarbonyl (6)-9 Me pentyl 2-phenylethyl Trichloromethylcarbonyl(6)-10 Me pentyl 2-phenylethyl 9-fluorenylmethyloxycarbonyl (6)-11 Mepentyl 2-phenylethyl 2-(trimethylsilyl)ethoxycarbonyl (6)-12 Me2-phenylethyl pentyl p-methoxybenzyl (6)-13 Me 2-phenylethyl octylp-methoxybenzyl (6)-14 Me 2-(2-thienyl)ethyl 2-cyclohexylethylp-methoxybenzyl (6)-15 Me 2-cyclohexylethyl 2-(2-thienyl)ethylp-methoxybenzyl (6)-16 Me Phenyl 1-methylpentyl p-methoxybenzyl (6)-17Me Me 2-phenylethyl p-methoxybenzyl (6)-18 Me Ethyl 2-phenylethylp-methoxybenzyl (6)-19 Me propyl 2-phenylethyl p-methoxybenzyl (6)-20 Mebutyl 2-phenylethyl p-methoxybenzyl (6)-21 Me hexyl 2-phenylethylp-methoxybenzyl (6)-22 Me heptyl 2-phenylethyl p-methoxybenzyl (6)-23 Meoctyl 2-phenylethyl p-methoxybenzyl (6)-24 Me 2-ethylhexyl 2-phenylethylp-methoxybenzyl (6)-25 Me nonyl 2-phenylethyl p-methoxybenzyl (6)-26 Medecyl 2-phenylethyl p-methoxybenzyl (6)-27 Me 3,7-dimethyloctyl2-phenylethyl p-methoxybenzyl (6)-28 Me undecyl 2-phenylethylp-methoxybenzyl (6)-29 Me 1-methylpentyl 2-phenylethyl p-methoxybenzyl(6)-30 Me p-butylphenyl 2-phenylethyl p-methoxybenzyl (6)-31 Me2-ethylhexyl 2-phenylethyl p-methoxybenzyl (6)-32 Me2-perfluorophenylethyl 2-phenylethyl p-methoxybenzyl (6)-33 Et2-perfluorophenylethyl 2-phenylethyl p-methoxybenzyl (6)-34 Propyl2-(2-thienyl)ethyl 2-phenylethyl p-methoxybenzyl (6)-35 Isopropyl2-cyclohexylethyl 2-phenylethyl p-methoxybenzyl (6)-36 butyl dodecyl2-phenylethyl p-methoxybenzyl (6)-37 tert-butyl Tridecyl 2-phenylethylp-methoxybenzyl (6)-38 benzyl tetradecyl 2-phenylethyl p-methoxybenzyl(6)-39 octyl butoxypropyl 2-phenylethvl p-methoxybenzyl (6)-40 allylmethoxylhexyl 2-phenylethyl p-methoxybenzyl (6)-41 methoxyethyl pentyl2-phenylethyl p-methoxybenzyl (6)-42 Ethoxyethyl pentyl 2-phenylethylp-methoxybenzyl (6)-43 2-ethylhexyl pentyl 2-phenylethyl p-methoxybenzyl(6)-44 isobutyl pentyl 2-phenylethyl p-methoxybenzyl (6)-45 hexyl pentyl2-phenylethyl p-methoxybenzyl (6)-46 Cyclohexyl pentyl 2-phenylethylp-methoxybenzyl (6)-47 2-phenylethyl pentyl 2-phenylethylp-methoxybenzyl (6)-48 dodecyl pentyl 2-phenylethyl p-methoxybenzyl(6)-49 2,2,2-trifluoromethyl pentyl 2-phenylethyl p-methoxybenzyl (6)-502-(trimethylsilyl)ethyl pentyl 2-phenylethyl p-methoxybenzyl (6)-51pentyl pentyl 2-phenylethyl p-methoxybenzyl (6)-52 2-bromoethyl pentyl2-phenylethyl p-methoxybenzyl (6)-53 Isopentyl pentyl 2-phenylethylp-methoxybenzyl (6)-54 2-chloroethyl pentyl 2-phenylethylp-methoxybenzyl (6)-55 Me pentyl 2-phenylethyl benzyl (6)-56 Me pentyl2-phenylethyl 2-methoxybenzyl (6)-57 Me pentyl 2-phenylethyl2,4-dimethoxybenzyl (6)-58 Me pentyl 2-phenylethyl3,4,5-trimethoxybenzyl (6)-59 Me pentyl 2-phenylethyl3,4-dimethoxybenzyl

indicates data missing or illegible when filed

Formula (7)

Examples of the compound represented by the formula (7) are shown below,but the compound represented by the formula (7) is not limited thereto.(7)-1 to (7)-54 in Table below show combinations of R¹¹, R¹⁴, R³¹, andR⁵¹ shown in each basic skeleton below. In Table below, “Me” representsa methyl group, and “Et” represents an ethyl group.

R⁸¹ and R⁸² in the basic skeletons shown below each independentlyrepresent a substituent selected from the group consisting of a hydrogenatom, a cyano group, a fluorine atom, a chlorine atom, a bromine atom,an iodine atom, a trifluoromethyl group, a trifluoromethoxy group, atrichloromethyl group, a trichloromethoxy group, a 2-thiazolyl group, a5-thiazolyl group, a 2-thienyl group, a 3-thienyl group, a styryl group,a 2-thiazolylvinyl group, a 5-thiazolylvinyl group, a 2-thienylvinylgroup, a 3-thienylvinyl group, a phenylethynyl group, a2-thiazolylethynyl group, a 5-thiazolylethynyl group, a 2-thienylethynylgroup, a 3-thienylethynyl group, a trimethylsilylethynyl group, atriethylsilylethynyl group, a triisopropylethynyl group, and a 1-octynylgroup. Herein, at least one of R⁸¹ or R⁸² represents a group other thanhydrogen.

TABLE 4 No.

(7)-1 Me pentyl 2-phenylethyl (7)-2 Me pentyl 2-(2-thienyl)ethyl (7)-3Me pentyl 2-pentafluorophenylethyl (7)-4 Me pentyl benzyl (7)-5 Mepentyl 3-propylphenyl (7)-6 Me pentyl octyl (7)-7 Me pentyl decyl (7)-8Me pentyl dodecyl (7)-9 Me 2-phenylethyl 2-cyclohexylethyl (7)-10 Me2-phenylethyl 1-methylpentyl (7)-11 Me 2-phenylethyl 1-methyloctyl(7)-12 Me 2-phenylethyl pentyl (7)-13 Me 2-perfluorophenylethyl octyl(7)-14 Me 2-(2-thienyl)ethyl 2-cyclohexylethyl (7)-15 Me2-cyclohexylethyl 2-(2-thienyl)ethyl (7)-16 Me Phenyl 1-methylpentyl(7)-17 Me Me 2-phenylethyl (7)-18 Me Ethyl 2-phenylethyl (7)-19 Mepropyl 2-phenylethyl (7)-20 Me butyl 2-phenylethyl (7)-21 Me hexyl2-phenylethyl (7)-22 Me heptyl 2-phenylethyl (7)-23 Me octyl2-phenylethyl (7)-24 Me 2-ethylhexyl 2-phenylethyl (7)-25 Me nonyl2-phenylethyl (7)-26 Me decyl 2-phenylethyl (7)-27 Me 3,7-dimethyloctyl2-phenylethyl (7)-28 Me undecyl 2-phenylethyl (7)-29 Me 1-methylpentyl2-phenylethyl (7)-30 Me p-butylphenyl 2-phenylethyl (7)-31 Me2-ethylhexyl 2-phenylethyl (7)-32 Me 2-perfluorophenylethyl2-phenylethyl (7)-33 Et 2-perfluorophenylethyl 2-phenylethyl (7)-34propyl 2-(2-thienyl)ethyl 2-phenylethyl (7)-35 Isopropyl2-cyclohexylethyl 2-phenylethyl (7)-36 butyl dodecyl 2-phenylethyl(7)-37 tert-butyl Tridecyl 2-phenylethyl (7)-38 benzyl tetradecyl2-phenylethyl (7)-39 octyl butoxypropyl 2-phenylethyl (7)-40 allylmethoxylhexyl 2-phenylethyl (7)-41 methoxyethyl pentyl 2-phenylethyl(7)-42 Ethoxyethyl pentyl 2-phenylethyl (7)-43 2-ethylhexyl pentyl2-phenylethyl (7)-44 isobutyl pentyl 2-phenylethyl (7)-45 hexyl pentyl2-phenylethyl (7)-46 Cyclohexyl pentyl 2-phenylethyl (7)-472-phenylethyl pentyl 2-phenylethyl (7)-48 dodecyl pentyl 2-phenylethyl(7)-49 2,2,2-trifluoromethyl pentyl 2-phenylethyl (7)-502-(trimethylsilyl)ethyl pentyl 2-phenylethyl (7)-51 pentyl pentyl2-phenylethyl (7)-52 2-bromoethyl pentyl 2-phenylethyl (7)-53 Isopentylpentyl 2-phenylethyl (7)-54 2-chloroethyl pentyl 2-phenylethyl

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Step Y1

The step Y1 is a step of reacting a compound represented by formula (1)with a first amine compound represented by formula (3) to obtain acompound represented by formula (4) below. Specifically, the step Y1 ispreferably a step of heating a composition including a compoundrepresented by formula (1) and a first amine compound represented byformula (3) to obtain a compound represented by formula (4).

Through the above step Y1, an amidation reaction of —COOR¹¹, —COOR¹²,—COOR¹³, and/or —COOR¹⁴ in the compound represented by the formula (1)with the first amine compound can be caused. If necessary, the obtainedcrude product is purified by separation and purification means includingwashing, extraction, drying, filtration, concentration,recrystallization, reprecipitation, crystallization, centrifugation,adsorption, and/or column purification to obtain the compoundrepresented by the formula (4).

The amount of the first amine compound used and represented by theformula (3) is preferably 1.0 to 10 molar equivalents and morepreferably 1.0 to 5.0 molar equivalents relative to 1 molar equivalentof the compound represented by the formula (1).

The composition may include a solvent.

A single solvent may be used, or two or more solvents may be used in amixed manner.

Non-limiting examples of the solvent include hydrocarbon solvents, ethersolvents, amide solvents, alcohol solvents, nitrile-based solvents, andsulfoxide solvents.

Examples of the hydrocarbon solvent include pentane, hexane, heptane,octane, decane, toluene, ethylbenzene, xylene, diethylbenzene,fluorobenzene, trifluoromethylbenzene, chlorobenzene, chloroform,dichloromethane, 1,1,2,2-tetrachloroethane, 1,1,2-trichloroethane,dichlorobenzene, trichlorobenzene, mesitylene, amylbenzene, decalin,1-methylnaphthalene, 1-ethylnaphthalene, 1-chloronaphthalene,1-fluoronaphthalene, 1,6-dimethylnaphthalene, benzonitrile,nitrobenzene, and tetralin.

Examples of the ether solvent include anisole, diethyl ether, dibutylether, diisopropyl ether, cyclopentyl methyl ether, diphenyl ether,tetrahydropyran, dioxane, dimethoxyethane, diethoxyethane, andtetrahydrofuran.

Examples of the amide solvent include N,N-dimethylformamide,N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolidinone,and N,N-dimethylacetamide.

Examples of the alcohol solvent include methanol, ethanol, propanol,isopropanol, amyl alcohol, benzyl alcohol, ethylene glycol, diethyleneglycol, propylene glycol, and glycerol.

Examples of the nitrile-based solvent include acetonitrile,propionitrile, and benzonitrile.

Examples of the sulfoxide solvent include dimethyl sulfoxide andsulfolane.

In particular, the solvent is preferably a solvent having a boilingpoint of 70° C. or higher and more preferably a solvent having a boilingpoint of 90° C. or higher.

Examples of the solvent having a boiling point of 90° C. or higherinclude heptane, octane, decane, toluene, ethylbenzene, xylene,diethylbenzene, fluorobenzene, trifluoromethylbenzene, chlorobenzene,dichlorobenzene, trichlorobenzene, mesitylene, amylbenzene, decalin,1-methylnaphthalene, 1-ethylnaphthalene, 1-chloronaphthalene,1-fluoronaphthalene, 1,6-dimethylnaphthalene, 1,1,2,2-tetrachloroethane,1,1,2-trichloroethane, nitrobenzene, benzonitrile, tetralin, anisole,dibutyl ether, cyclopentyl methyl ether, diphenyl ether, dioxane,diethoxyethane, N,N-dimethylformamide, N-methylpyrrolidone,N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolidinone,N,N-dimethylacetamide, 1-propanol, 1-butanol, isobutyl alcohol,2-butanol, amyl alcohol, benzyl alcohol, ethylene glycol, diethyleneglycol, propylene glycol, glycerol, dimethyl sulfoxide, and sulfolane.

When the composition includes a solvent, the content of the solvent ispreferably 75.0 to 99.9 mass % and more preferably 80.0 to 98.0 mass %relative to the total mass of the composition.

The reaction temperature is not particularly limited, but is preferably20° C. to 250° C. and more preferably 50° C. to 200° C.

The reaction time varies depending on the solvent used and the reactionconditions including a reaction temperature, but is normally 1 to 24hours and preferably 1 to 20 hours.

Step Y2

The step Y2 is a step of reacting the compound represented by theformula (4) with a first amine compound represented by formula (5) toobtain a compound represented by formula (6). Specifically, the step Y2is preferably a step of heating a composition including the compoundrepresented by the formula (4) and a second amine compound representedby formula (5) to obtain a compound represented by formula (6).

Through the step Y2, an amidation/imidation reaction between twoadjacent ester groups (—COOR¹² and —COOR¹³) in the compound representedby the formula (4) and the second amine compound is caused to form animide bond.

The amount of the second amine compound used and represented by theformula (5) is preferably 1.0 to 10.0 molar equivalents and morepreferably 1.0 to 5.0 molar equivalents relative to 1 molar equivalentof the compound represented by the formula (4).

The composition may include a solvent.

A single solvent may be used, or two or more solvents may be used in amixed manner.

The solvent is not particularly limited. For example, the solventsdescribed in the step Y1 are exemplified, and preferred forms thereofare also the same.

When the composition includes a solvent, the content of the solvent ispreferably 75.0 to 99.9 mass % and more preferably 80.0 to 98.0 mass %relative to the total mass of the composition.

The reaction temperature is not particularly limited, but is preferably20° C. to 250° C. and more preferably 50° C. to 200° C.

The reaction time varies depending on the solvent used and the reactionconditions including a reaction temperature, but is normally 1 to 24hours and preferably 1 to 20 hours.

After completion of the reaction, if necessary, the obtained compoundrepresented by the formula (6) may be purified by separation andpurification means including washing, extraction, drying, filtration,concentration, recrystallization, reprecipitation, crystallization,centrifugation, column purification, adsorption, and/or sublimationpurification.

Step Y3

The step Y3 is a step of removing (deprotecting) P³¹ serving as aprotecting group from the compound represented by the formula (6) toobtain a compound represented by formula (7).

Examples of the deprotection method include a method for performingdeprotection using a deprotecting reagent under acidic or basicconditions, a method for performing deprotection using an oxidizingagent, a method for performing deprotection using a Lewis acid, a methodfor performing deprotection using a nucleophile, a method for causing areductive deprotection reaction (hydrogenolysis) in the presence of ametal catalyst, and a method for performing deprotection using zincunder acidic conditions.

Examples of the deprotecting reagent under acidic conditions includeacids such as hydrochloric acid, hydrogen bromide/acetic acid, sulfuricacid, formic acid, methanesulfonic acid, p-toluenesulfonic acid, andtrifluoroacetic acid. In particular, when the protecting grouprepresented by P³¹ is a (hetero)arylmethyl group such as a methoxybenzylgroup, sulfonic acids such as sulfuric acid, methanesulfonic acid, andp-toluenesulfonic acid are preferred.

The deprotecting reagent under basic conditions may be either aninorganic base or an organic base. Examples of the inorganic baseinclude hydroxides of alkali metals or alkaline earth metals,carbonates, and hydrogencarbonates. Examples of the organic base includeamines such as triethylamine, diisopropylethylamine, piperidine,N-methylmorpholine, dimethylaminopyridine, DBU(1,8-diazabicyclo[5.4.0]-7-undecene), and DBN(1.5-diazabicyclo[4.3.0]non-5-ene; pyridine; and imidazole.

An example of the oxidizing agent is2,3-dichloro-5,6-dicyano-p-benzoquinone.

Examples of the Lewis acid include trimethylsilyltrifluoromethanesulfonate, iodotrimethylsilane, boron trichloride, andtin(IV) chloride.

Examples of the nucleophile include thiol compounds (e.g.,benzenethiol), cesium fluoride, and fluoride ions such astetraalkylammonium fluoride.

Examples of the metal catalyst used as a deprotecting reagent includepalladium catalysts (e.g., palladium carbon, palladium carbon hydroxide,and palladium oxide), platinum catalysts (e.g., platinum carbon andplatinum oxide), rhodium catalysts (e.g., rhodium carbon), and rutheniumcatalysts (e.g., ruthenium carbon).

The deprotection reaction is preferably performed in the presence of asolvent.

A single solvent may be used, or two or more solvents may be used in amixed manner.

The solvent is not particularly limited. For example, the solventsdescribed in the step Y1 are exemplified. Alternatively, an estersolvent (e.g., methyl acetate, ethyl acetate, propyl acetate, butylacetate, and isobutyl acetate) or a ketone solvent (e.g., acetone,2-butanone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone,isophorone, and acetophenone) may be used. In the case of using an acidand a base, water alone or a mixture of water and a solvent may be used.

The step Y3 and a step Y4 described later may be simultaneouslyperformed. Specifically, for example, a method in which a compositionincluding a deprotecting reagent, a compound represented by formula (6),and a solvent is heated is employed.

Step Y4

The step Y4 is a step of obtaining a compound represented by formula (2)from the compound represented by the formula (7). Specifically, the stepY4 is preferably a step of heating a composition including the compoundrepresented by the formula (7) to obtain a compound represented byformula (2).

Through the above step Y4, an imidation reaction between —COOR¹⁴ and anamide group in the compound represented by the formula (7) is caused toobtain a compound represented by formula (2).

The composition may include a solvent.

A single solvent may be used, or two or more solvents may be used in amixed manner.

The solvent is not particularly limited. For example, the solventsdescribed in the step Y1 are exemplified, and preferred forms thereofare also the same.

When the composition includes a solvent, the content of the solvent ispreferably 75.0 to 99.9 mass % and more preferably 80.0 to 98.0 mass %relative to the total mass of the composition.

The reaction temperature is not particularly limited, but is preferably20° C. to 250° C. and more preferably 50° C. to 200° C.

The reaction time varies depending on the solvent used and the reactionconditions including a reaction temperature, but is normally 1 to 24hours and preferably 1 to 20 hours.

After completion of the reaction, if necessary, the obtained compoundrepresented by the formula (7) may be purified by separation andpurification means including washing, extraction, drying, filtration,concentration, recrystallization, reprecipitation, crystallization,centrifugation, column purification, adsorption, and/or sublimationpurification, and is preferably purified by separation and purificationmeans including sublimation purification.

As described above, the compound represented by the formula (1) ispreferably the compound represented by the formula (8), and the compoundrepresented by the formula (2) is preferably the compound represented bythe formula (9).

Hereafter, a preferred embodiment (hereafter, also referred to as“second embodiment-1”) of the method for producing the compoundrepresented by the formula (9) from the compound represented by theformula (8) (the formula (11A) shown later corresponds to the formula(8)).

Preferred Embodiment of Method for Producing Compound Represented byFormula (9) (Second Embodiment-1)

The production method in the second embodiment-1 includes steps Y1′ toY4′ below.

Step Y1′: a step of reacting a compound represented by formula (X1)below with a compound represented by formula (X2) below to obtain acomposition including a compound represented by formula (11A) and acompound represented by formula (11B), and then reacting the compositionwith a first amine compound represented by formula (12) withoutsubjecting the composition to column purification to obtain a compoundrepresented by formula (13)

Step Y2′: a step of reacting the compound represented by the formula(13) with a second amine compound represented by formula (14) below toobtain a compound represented by formula (15) below

Step Y3′: a step of removing P³¹ serving as a protecting group from thecompound represented by the formula (15) to obtain a compoundrepresented by formula (16) below

Step Y4′: a step of obtaining a compound represented by the formula (9)from the compound represented by the formula (16)

The production method according to the second embodiment-1 preferablyfurther includes a step Y0′ below.

Step Y0′: a step of further purifying the compound represented by theformula (X2) before reacting the compound represented by the formula(X1) with the compound represented by the formula (X2)

Hereafter, first, the compounds represented by the formulae (X1), (X2),(11A), (11B), and (12) to (16) will be described, and then theprocedures of the steps Y0′ to Y4′ will be described.

Compounds Represented by Formulae (X1), (X2), (11A), (11B), and (12) to(16)

In the formula (X1), X¹ to X⁴ each represent a halogen atom or—CO—O—R¹⁰¹. R¹⁰¹ represents an aliphatic hydrocarbon group, an arylgroup, or a heteroaryl group. One of X¹ and X⁴ represents a halogenatom, and the other represents —CO—O—R¹⁰¹. One of X² and X³ represents ahalogen atom, and the other represents —CO—O—R¹⁰¹.

Furthermore, from the viewpoint of ease of production of raw materials,it is preferable that X² and X⁴ of the compound represented by theformula (X1) represent —CO—O—R¹⁰¹ and X¹ and X³ represent a halogenatom.

Two R¹⁰¹ present in the formula (X1) preferably each represent analiphatic hydrocarbon group or each represent an aryl or heteroarylgroup, and more preferably each represent an aliphatic hydrocarbongroup.

The aliphatic hydrocarbon group, aryl group, and heteroaryl grouprepresented by R¹⁰¹ in the formula (X1) are the same as the aliphatichydrocarbon group, aryl group, and heteroaryl group represented by R¹¹to R¹⁴ in the formula (1), and preferred forms thereof are also thesame.

R⁸¹ to R⁸⁶ respectively have the same meaning as R⁸¹ to R⁸⁶ in theformula (8), and preferred forms thereof are also the same.

In the formula (X2), R¹⁰¹ represents an aliphatic hydrocarbon group, anaryl group, or a heteroaryl group. The aliphatic hydrocarbon group, arylgroup, and heteroaryl group represented by R¹⁰¹ in the formula (X2) arethe same as the aliphatic hydrocarbon group, aryl group, and heteroarylgroup represented by R¹¹ to R¹⁴ in the formula (1), and preferred formsthereof are also the same.

In the formula (X2), R¹⁰¹ more preferably represents an aryl group or aheteroaryl group.

The compound represented by the formula (X2) is preferably aryl formateor heteroaryl formate and more preferably an aryl formate substitutedwith an electron-withdrawing group.

In the formula (11A), X⁵ to X⁸ each independently represent —CO—O—R¹⁰¹.Herein, R¹⁰¹ in X⁵ is different from R¹⁰¹ in X⁸. That is, one of R¹⁰¹ inX⁵ and R¹⁰¹ in X⁸ represents an aliphatic hydrocarbon group, and theother represents an aryl group or a heteroaryl group. R¹⁰¹ in X⁶ is alsodifferent from R¹⁰¹ in X⁷. That is, one of R¹⁰¹ in X⁶ and R¹⁰¹ in X⁷represents an aliphatic hydrocarbon group, and the other represents anaryl group or a heteroaryl group.

The aliphatic hydrocarbon group, aryl group, and heteroaryl grouprepresented by R¹⁰¹ in X⁵ to X⁸ are the same as the aliphatichydrocarbon group, aryl group, and heteroaryl group represented by R¹¹to R¹⁴ in the formula (1), and preferred forms thereof are also thesame.

R⁸¹ to R⁸⁶ respectively have the same meaning as R⁸¹ to R⁸⁶ in theformula (8), and preferred forms thereof are also the same.

In the formula (11A), preferably, R¹⁰¹ in X⁶ and X⁸ represents analiphatic hydrocarbon group, and R¹⁰¹ in X⁵ and X⁷ represents an arylgroup or a heteroaryl group.

R⁸¹ to R⁸⁶ respectively have the same meaning as R⁸¹ to R⁸⁶ in theformula (8), and preferred forms thereof are also the same.

In the formula (11B), one of X⁹ and X¹⁰ represents a hydrogen atom, andthe other represents —CO—O—R¹⁰¹. R¹⁰¹ has the same meaning as R¹⁰¹ inthe formula (X1), and preferred forms thereof are also the same. X⁶ andX⁷ respectively have the same meaning as X⁶ and X⁷ in the formula (11A),and preferred forms thereof are also the same.

R⁸¹ to R⁸⁶ respectively have the same meaning as R⁸¹ to R⁸⁶ in theformula (8), and preferred forms thereof are also the same.

In the formula (11B), preferably, X⁹ represents a hydrogen atom and X¹⁰represents —CO—O—R¹⁰¹. R¹⁰¹ in X¹⁰ and R¹⁰¹ in X⁶ preferably eachrepresent an aliphatic hydrocarbon group or each represent an aryl orheteroaryl group, and more preferably each represent an aliphatichydrocarbon group.

The formula (12) has the same meaning as the formula (3) describedabove, and preferred forms thereof are also the same. In the formula(12), R³¹ represents a substituent. P³¹ represents a protecting group.

In the formula (13), one of X¹¹ and X¹² represents —CO—O—R¹⁰¹, and theother represents —CO—N(R³¹)(P³¹). R¹⁰¹ has the same meaning as R¹⁰¹ inthe formula (X1), and preferred forms thereof are also the same. R³¹ andP³¹ respectively have the same meaning as R³¹ and P³¹ in the formula(12). X⁶ and X⁷ respectively have the same meaning as X⁶ and X⁷ in theformula (11A), and preferred forms thereof are also the same. R⁸¹ to R⁸⁶respectively have the same meaning as R⁸¹ to R⁸⁶ in the formula (8), andpreferred forms thereof are also the same.

In the formula (13), preferably, X¹¹ represents —CO—N(R³¹)(P³¹) and X¹²represents —CO—O—R¹⁰¹.

The formula (14) has the same meaning as the formula (5) describedabove, and preferred forms thereof are also the same. In the formula(13), R⁵¹ represents a substituent.

In the formula (15), X¹¹ and X¹² respectively have the same meaning asX¹¹ and X¹² in the formula (13). R⁵¹ has the same meaning as R⁵¹ in theformula (14). R⁸¹ to R⁸⁶ respectively have the same meaning as R⁸¹ toR⁸⁶ in the formula (8), and preferred forms thereof are also the same.

In the formula (16), one of X¹³ and X¹⁴ represents —CO—O—R¹⁰¹, and theother represents —CO—N(R³¹)(H). R⁵¹ has the same meaning as R⁵¹ in theformula (14). R¹⁰¹ has the same meaning as R¹⁰¹ in the formula (X1), andpreferred forms thereof are also the same. R⁸¹ to R⁸⁶ respectively havethe same meaning as R⁸¹ to R⁸⁶ in the formula (8), and preferred formsthereof are also the same.

In the formula (16), preferably, X¹³ represents —CO—N(R³¹)(H) and X¹⁴represents —CO—O—R¹⁰¹.

Step Y1′

Step Y1′ is a step of reacting a compound represented by formula (X1)with a compound represented by formula (X2) to obtain a compositionincluding a compound represented by formula (11A) and a compoundrepresented by formula (11B), and then reacting the composition with afirst amine compound represented by formula (12) without subjecting thecomposition to column purification to obtain a compound represented byformula (13). The compound represented by the formula (11A) correspondsto the compound represented by the formula (8).

In the step Y1′, the compound represented by the formula (11B) is aby-product formed in a synthesis reaction of reacting the compoundrepresented by the formula (X1) with the compound represented by theformula (X2) to obtain the compound represented by the formula (11A).The formation of the compound represented by the formula (11B) as aby-product is probably caused by formic acid that may be included as animpurity in the compound represented by the formula (X2) (the compoundrepresented by the formula (X2) is, for example, 2,4,6-trichlorophenylformate). In the step Y1′, the formation of the compound represented bythe formula (11B) as a by-product can be suppressed by performing thestep (step Y0′) of purifying the compound represented by the formula(X2) before the reaction of the compound represented by the formula (X1)with the compound represented by the formula (X2).

The purification method in the step Y0′ is not particularly limited, butis separation and purification means including washing, extraction,drying, filtration, concentration, recrystallization, reprecipitation,crystallization, centrifugation, column purification, adsorption, and/orsublimation purification. Among them, recrystallization,reprecipitation, or crystallization is preferred, and recrystallizationis particularly preferred.

The reaction of the compound represented by the formula (X1) and thecompound represented by the formula (X2) is not particularly limited,and a cross-coupling process in the presence of a transition metalcatalyst can be applied.

The use amounts of the compound represented by the formula (X1) and thecompound represented by the formula (X2) in the coupling reaction arenot particularly limited. The amount of the compound represented by theformula (X2) is preferably 1.0 to 15.0 molar equivalents, morepreferably 1.0 to 10.0 molar equivalents, and further preferably 1.0 to5.0 molar equivalents relative to 1 molar equivalent of the halogen atomof the compound represented by the formula (X1).

Non-limiting examples of the transition metal catalyst include apalladium catalyst (palladium(0) catalyst or palladium(II) catalyst), anickel catalyst (nickel(0) catalyst), an iron catalyst (iron(III)catalyst), a cobalt catalyst (cobalt(II) catalyst), and an iridiumcatalyst (iridium(0) catalyst). In particular, a palladium catalyst or anickel catalyst is preferable, and a palladium catalyst is morepreferable.

Non-limiting examples of the palladium catalyst include palladiumacetate, tris(dibenzylideneacetone)dipalladium(0) chloroform complex,tetrakis(triphenylphosphine)palladium(0), anddichlorobis[di-tert-butyl(4-dimethylaminophenyl)phosphine]palladium(II).

The amount of the transition metal catalyst used in the couplingreaction is not particularly limited as long as it is an amount actingas a catalyst, but is preferably 0.001 to 1.0 molar equivalents and morepreferably 0.01 to 0.5 molar equivalents relative to 1 molar equivalentof the halogen atom of the compound represented by the formula (X1).

The coupling reaction may be performed with addition of a ligand. Theligand is not particularly limited. For example, ligands described inACCOUNTS OF CHEMICAL RESEARCH 2008, 41, 1461-1473; Angew. Chem. Int. Ed.2008, 47, 6338-6361; Angew. Chem. Int. Ed. 2008, 47, 6338-6361; Journalof Synthetic Organic Chemistry Japan 2001, 59, 607-616; AldrichimicaActa 2006, 39, 17.(b); and Schlummer, B.; Scholz, U. Adv. Synth. Catal.2004, 346, 1599 can be used.

The coupling reaction may be performed in the presence of a base.

Examples of the base include organic bases and inorganic bases, andorganic bases are preferred. Examples of the organic base includetertiary amines (e.g., trimethylamine, dimethylisopropylamine,—N,N,N′,N′-tetramethyldiaminomethane,—N,N,N′,N′-tetramethylethylenediamine, triethylamine,diisopropylethylamine, tripropylamine, tributylamine, tripentylamine,triheptylamine, trioctylamine, diazabicycloundecene, diazabicyclononene,and 1,4-diazabicyclo[2.2.2]octane) and pyridines (e.g., pyridine,2,6-lutidine, quinoline, and isoquinoline). Examples of the inorganicbase include hydroxides, carbonates, phosphates, and acetates. Specificexamples of the inorganic base include sodium hydroxide, potassiumhydroxide, cesium hydroxide, sodium carbonate, potassium carbonate,cesium carbonate, sodium phosphate, potassium phosphate, and sodiumacetate.

The bases may be used alone or in combination of two or more.

The amount of the base used is not particularly limited, but ispreferably 1.0 to 15 molar equivalents, more preferably 1.0 to 10 molarequivalents, and further preferably 1.1 to 2.0 molar equivalentsrelative to 1 molar equivalent of the compound represented by theformula (X2).

The coupling reaction may be performed in the presence of a solvent. Asingle solvent may be used, or two or more solvents may be used in amixed manner.

The solvent is not particularly limited, and a solvent used for atransition metal catalytic reaction can be used. Examples of the solventinclude a hydrocarbon solvent, an ether solvent, an amide solvent, anester solvent, a nitrile solvent, a ketone solvent, and a sulfoxidesolvent.

Examples of the hydrocarbon solvent include pentane, hexane, heptane,octane, decane, toluene, ethylbenzene, xylene, diethylbenzene,fluorobenzene, trifluoromethylbenzene, chloroform, dichloromethane,1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene,dichlorobenzene, trichlorobenzene, mesitylene, amylbenzene, decalin,1-methylnaphthalene, 1-ethylnaphthalene, 1-chloronaphthalene,1-fluoronaphthalene, 1,6-dimethylnaphthalene, nitrobenzene,benzonitrile, and tetralin.

Examples of the ether solvent include anisole, diethyl ether, dibutylether, diisopropyl ether, cyclopentyl methyl ether, diphenyl ether,tetrahydropyran, dioxane, dimethoxyethane, diethoxyethane, andtetrahydrofuran.

Examples of the amide solvent include N,N-dimethylformamide,N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolidinone,and N,N-dimethylacetamide.

Examples of the ester solvent include methyl acetate, ethyl acetate,propyl acetate, butyl acetate, and isobutyl acetate.

Examples of the nitrile solvent include acetonitrile, propionitrile, andbenzonitrile.

Examples of the ketone solvent include acetone, 2-butanone, methylisobutyl ketone, diisobutyl ketone, cyclohexanone, isophorone, andacetophenone.

Examples of the sulfoxide solvent include dimethyl sulfoxide andsulfolane.

The coupling reaction may be performed in an inert gas atmosphere.Examples of the inert gas include nitrogen, helium, and argon.

The reaction temperature of the coupling reaction is not particularlylimited, but is preferably 0° C. to 200° C. and more preferably 50° C.to 150° C.

The reaction time of the coupling reaction varies depending on thesolvent used and the reaction conditions including a reactiontemperature, but is normally 1 to 24 hours and preferably 3 to 20 hours.

In the step Y1′, a step of reacting a composition obtained through acoupling reaction of the compound represented by the formula (X1) andthe compound represented by the formula (X2) with the first aminecompound represented by the formula (12) is performed without columnpurification. From the viewpoint of further improving the purity of thecompound represented by the formula (9), which is a target compound, thecomposition includes at least the compound represented by the formula(11A), and the content of the compound represented by the formula (11B)is preferably 3.0 mass % or less and more preferably 1.0 mass % or lessrelative to the total solid content of the composition. When the stepY0′ is performed, the content of the compound represented by the formula(11B) in the composition of the step Y1′ can be adjusted to 3.0 mass %or less relative to the total solid content of the composition.

The lower limit of the content of the compound represented by theformula (11B) is usually 0 mass % or more and often 0.01 mass % or morerelative to the total solid content of the composition.

The term “solid content” refers to components in a composition fromwhich solvents are removed. Even if components other than solvents inthe composition are liquid, the components are regarded as solidcontents.

If necessary, the composition may be purified by separation andpurification means other than column purification (such as washing,extraction, drying, filtration, concentration, recrystallization,reprecipitation, crystallization, adsorption, and centrifugation) aftercompletion of the coupling reaction.

Specifically, the step of reacting the composition with the first aminecompound represented by the formula (12) is preferably a step of addingthe first amine compound represented by the formula (12) to thecomposition and heating the mixture to obtain the compound representedby the formula (13).

The specific procedure is the same as that of the step Y1 of theproduction method in the second embodiment described above, and thepreferred form is also the same.

Step Y2′

The step Y2′ is the same as the step Y2 of the production method in thesecond embodiment described above, and the preferred form is also thesame.

Step Y3′

The step Y3′ is the same as the step Y3 of the production method in thesecond embodiment described above, and the preferred form is also thesame.

Step Y4′

The step Y4′ is the same as the step Y4 of the production method in thesecond embodiment described above, and the preferred form is also thesame.

Composition

The present invention also relates to a composition.

The composition according to an embodiment of the present invention is acomposition used for synthesizing the above-described compoundrepresented by the formula (9).

The composition includes at least the above-described compoundrepresented by the formula (8).

In the composition, the total content of a compound represented byformula (17) below and a compound represented by formula (18) below is3.0 mass % or less relative to the total solid content of thecomposition.

The term “solid content” refers to components in a composition fromwhich solvents are removed. Even if components other than solvents inthe composition are liquid, the components are regarded as solidcontents.

In the formulae (17) and (18), R¹¹ to R¹⁴ each independently representan aliphatic hydrocarbon group, an aryl group, or a heteroaryl group.One of R¹² and R¹³ represents an aliphatic hydrocarbon group, and theother represents an aryl group or a heteroaryl group.

R⁸¹ to R⁸⁶ respectively have the same meaning as R⁸¹ to R⁸⁶ in theformula (8), and preferred forms thereof are also the same.

The above composition is the same as the composition obtained byreacting the compound represented by the formula (X1) with the compoundrepresented by the formula (X2) in the step X′ in the production methodaccording to the first embodiment-1 and the composition obtained byreacting the compound represented by the formula (X1) and the compoundrepresented by the formula (X2) in the step Y1′ in the production methodaccording to the second embodiment-1. That is, the compound representedby the formula (8) corresponds to the compound represented by theformula (11A). The compounds represented by the formula (17) and theformula (18) are covered by the compound represented by the formula(11B). The compound represented by the formula (17) corresponds to aform in which X⁹ represents a hydrogen atom and X¹⁰ represents—CO—O—R¹⁰¹ in the compound represented by the formula (11B), and thecompound represented by the formula (18) corresponds to a form in whichX⁹ represents —CO—O—R¹⁰¹ and X¹⁰ represents a hydrogen atom in thecompound represented by the formula (11B).

The preferred form of the compound represented by the formula (8) is thesame as that of the compound represented by the formula (11A). Thepreferred form of the compound represented by the formula (17) is thesame as that of the compound represented by the formula (11B).

In the formula (18), R¹¹ and R¹³ preferably each represent an aliphatichydrocarbon group or each represent an aryl or heteroaryl group, andmore preferably each represent an aliphatic hydrocarbon group.

The lower limit of the total content of the compound represented by theformula (17) and the compound represented by the formula (18) in thecomposition is usually 0 mass % or more and often 0.01 mass % or morerelative to the total solid content of the composition.

In the composition, the content of the compound represented by theformula (8) is preferably 94.0 mass % or more, more preferably more than97.0 mass %, and further preferably 98.0 mass % or more relative to thetotal mass of the composition. The upper limit of the content of thecompound represented by the formula (8) in the composition is notparticularly limited, but is 100 mass % or less and preferably 99.99mass % or less.

Compound

The present invention also relates to a novel compound.

The compound according to an embodiment of the present invention is thecompound represented by the formula (4), the compound represented by theformula (6), the compound represented by the formula (7), a compoundrepresented by formula (11A′) below, and a compound represented byformula (11A″) below. Any of the compounds can be used as anintermediate compound for obtaining the compound represented by theformula (2).

Compound Represented by Formula (11A′)

Hereafter, the compound represented by the formula (11A′) will bedescribed. The compound represented by the formula (11A′) is a compoundcovered by the compound represented by the formula (11A). That is, inthe above-described compound represented by the formula (11A), at leastone of R⁸¹ to R⁸⁶ represents a substituent. Preferably, at least one ofR⁸¹ and R⁸² represents a substituent. More preferably, both R⁸¹ and R⁸²represent substituents.

The preferred form of the compound represented by the formula (11A′) isthe same as that of the compound represented by the formula (11A).

Examples of the compound represented by the formula (11A′) are shownbelow, but the compound represented by the formula (11A′) is not limitedthereto.

(8)-1 to (8)-43 in Table below show combinations of X⁵, X⁶, X⁷, X⁸, R⁸¹,and R⁸² shown in each basic skeleton below. In Table below, “Me”represents a methyl group, and “Et” represents an ethyl group.

In Table below, “ester” and “CO₂” are intended to indicate anoxycarbonyl group. That is, “2,4,6-trichlorophenylester” is intended toindicate “2,4,6-trichlorophenyloxycarbonyl”, and “CO₂Me” is intended toindicate “methoxycarbonyl”.

No. X⁵ X⁶ X⁷ X⁸ R⁸¹ R⁸² (8)-1  2,4.6- CO₂Me 2.4.6- CO₂Me F Ftrichlorophenylester trichlorophenylester (8)-2  2,4,6- CO₂Me 2.4.6-CO₂Me CF₃ CF₃ trichlorophenylester trichlorophenylester (8)-3  2,4.6-CO₂Me 2,4,6- CO₂Me CCl₃ CCl₃ trichlorophenylester trichlorophenylester(8)-4  2.4.6- CO₂Me 2.4,6- CO₂Me CN CN trichlorophenylestertrichlorophenylester (8)-5  2.4.6- trichlorophenylester CO₂Me 2,4.6-trichlorophenylester CO₂Me *—≡— Si(i-propyl)₃ * ≡ Si(i-propyl)₃ (8)-6 2.4.6- CO₂Me 2.4.6- CO₂Me Br Br trichlorophenylestertrichlorophenylester (8)-7  2,4.6- CO₂Me 2,4,6- CO₂Me H Brtrichlorophenylester trichlorophenylester (8)-8  2,4,6-trichlorophenylester CO₂Me 2,4.6- trichlorophenylester CO₂Me

(8)-9  2.4,6- trichlorophenylester CO₂Me 2.4.6- trichlorophenylesterCO₂Me

(8)-10 2.4.6- trichlorophenylester CO₂Me 2,4,6- trichlorophenylesterCO₂Me

(8)-11 2.4.6- trichlorophenylester CO₂Me 2.4.6- trichlorophenylesterCO₂Me Br

(8)-12 2.4.6- trichlorophenylester CO₂Me 2,4,6- trichlorophenylesterCO₂Me H

(8)-13 2.4.6- trichlorophenylester CO₂Me 2.4.6- trichlorophenylesterCO₂Me

(8)-14 2,4.6- trichlorophenylester CO₂Me 2,4,6- trichlorophenylesterCO₂Me

(8)-15 2.4.6- trichlorophenylester CO₂Me 2,4.6- trichlorophenylesterCO₂Me

(8)-16 2.4.6- CO₂Me 2.4.6- CO₂Me H CN trichlorophenylestertrichlorophenylester (8)-17 2,4.6- CO₂Me 2.4.6- CO₂Me H Ftrichlorophenylester trichlorophenylester (8)-18 2,4,6- CO₂Me 2.4,6-CO₂Me H CF₃ trichlorophenylester trichlorophenylester (8)-19 2.4,6-CO₂Me 2.4.6- CO₂Me H CCl₃ tiichlorophenylester trichlorophenylester(8)-20 2A.6- trichlorophenylester COMe 2,4.6- trichlorophenylester CO₂MeH

(8)-21 2.4.6- trichlorophenylester CO₂Me 2.4.6- trichlorophenylesterCO₂Me

(8)-22 2,4.6- trichlorophenylester CO₂Me 2,4.6- trichlorophenylesterCO₂Me

(8)-23 2,4,6- trichlorophenylester CO₂Me 2,4.6- trichlorophenylesterCO₂Me

(8)-24 2.4.6- trichlorophenylester CO₂Me 2.4,6- trichlorophenylesterCO₂Me

(8)-25 2.4.6- trichlorophenylester CO₂Me 2,4.6- trichlorophenyiesterCO₂Me

(8)-26 2,4,6- trichlorophenylester CO₂Me 2.4,6- trichlorophenylesterCO₂Me

(8)-27 2.4.6- trichlorophenylester CO,Me 2.4.6- trichlorophenylesterCO₂Me

(8)-28 2.4,6- CO₂Me 2.4.6- CO₂Me Cl Cl trichlorophenylestertrichlorophenylester (8)-29 2.4,6- CO₂Me 2.4.8- CO₂Me H Cltrichlorophenylester trichlorophenylester (8)-30 2.4.6- CO₂Me 2.4.6-CO₂Me I I trichlorophenylester trichlorophenylester (8)-31 2.4,6- CO₂Me2.4.6- CO₂Me H I trichlorophenylester trichlorophenylester (8)-32 2,4,6-trichlorophenylester CO₂Me 2.4.6- trichlorophenylester CO₂Me

(8)-33 2.4.6- trichlorophenylester CO₂Me 2.4.6- trichlorophenylesterCO₂Me

(8)-34 2.4,6- trichlorophenylester CO₂Me 2. 4.6- trichlorophenylesterCO₂Me

(8)-35 CO₂Me 2.4.6- CO₂Me 2.4.6- F F trichlorophenylestertrichlorophenyl- ester (8)-36 CO₂Me 2A,6- CO₂Me 2,4.6- CF₃ CF₃trichlorophenylester trichlorophenyl- ester (8)-37 CO₂Me 2,4,13- CO₂Me2.4.6- CCl₃ CCl₃ trichlorophenylester trichloropheny- lester (8)-38CO₂Me 2,4.6- CO₂Me 2.4.6- CN CN trichlorophenylester trichlorophenyl-ester (8)-39 2.4.6- CO₂Et 2.4.6- CO₂Et Br Br trichlorophenylestertrichlorophenylester (8)-40 2.4.6- CO₂C₄H₉ 2.4.6- CO₂C₄H₉ Cl Cltrichlorophenylester trichlorophenylester (8)-41 phenylester CO₂Mephenylester CO₂Me Br Br (8)-42 4-chlorophenylester CO₂Me4-chlorophenylester CO₂Me Br Br (8)-43 4-nitrophenylester CO₂Me4-nitrophenylester CO₂Me Br Br

Compound Represented by Formula (11A″)

Hereafter, the compound represented by the formula (11A″) will bedescribed. The compound represented by the formula (11A″) is a compoundcovered by the compound represented by the formula (11A).

In the formula (11A″), X⁵ to X⁸ each independently represent —CO—O—R¹⁰¹.Each R¹⁰¹ independently represents an aliphatic hydrocarbon group, anaryl group, or a heteroaryl group.

Herein, R¹⁰¹ in X⁵ and R¹⁰¹ in X⁸ are different from each other. One ofR¹⁰¹ in X⁵ and R¹⁰¹ in X⁸ represents an aliphatic hydrocarbon group, andthe other represents an aryl group or a heteroaryl group. Herein, R¹⁰¹in X⁶ and R¹⁰¹ in X⁷ are different from each other. One of R¹⁰¹ in X⁶and R¹⁰¹ in X⁷ represents an aliphatic hydrocarbon group, and the otherrepresents an aryl group or a heteroaryl group. In the case where thealiphatic hydrocarbon group represented by R¹⁰¹ is an aliphatichydrocarbon group having one carbon atom, the aryl group represented byR¹⁰¹ is an unsubstituted aryl group or an aryl group into which two orless substituents are introduced.

R⁸³ to R⁸⁶ each independently represent a hydrogen atom or asubstituent.

It has been confirmed that in the case where the aliphatic hydrocarbongroup represented by R¹⁰¹ has two or more carbon atoms, the solubilityof the compound is better compared with the case where the aliphatichydrocarbon group represented by R¹⁰¹ has one carbon atom, whichprovides synthetic advantages such as reduction in the amount ofreaction solvents and achieves higher yield in some cases.

The preferred form of the compound represented by the formula (11A″) isthe same as that of the compound represented by the formula (11A).

Examples of the compound represented by the formula (11A″) are shownbelow, but the compound represented by the formula (11A″) is not limitedthereto.

(9)-1 to (9)-38 in Table below show combinations of X⁵, X⁶, X⁷, and X⁸shown in each basic skeleton below. In Table below, “Me” represents amethyl group, and “Et” represents an ethyl group.

In Table below, “ester” and “CO₂” are intended to indicate anoxycarbonyl group. That is, “2,4,6-trichlorophenylester” is intended toindicate “2,4,6-trichlorophenyloxycarbonyl”, and “CO₂Me” is intended toindicate “methoxycarbonyl”.

No. X⁵ X⁶ X⁷ X⁸ (9)-1  2,4,6- CO₂Et 2,4,6- CO₂Et trichlorophenylestertrichlorophenylester (9)-2  2,4,6- trichlorophenylester

2,4,6- trichlorophenylester

(9)-3  2,4,6- CO₂n-C₃H₇ 2,4,6- CO₂n-C₃H₇ trichlorophenylestertrichlorophenylester (9)-4  2,4,6- CO₂n-C₄H₉ 2,4,6- CO₂n-C₄H₉trichlorophenylester trichlorophenylester (9)-5  2,4,6- CO₂n-C₅H₁₁2,4,6- CO₂n-C₅H₁₁ trichlorophenylester trichlorophenylester (9)-6 2,4,6- CO₂n-C₆H₁₃ 2,4,6- CO₂n-C₆H₁₃ trichlorophenylestertrichlorophenylester (9)-7  2,4,6- trichlorophenylester

2,4,6- trichlorophenylester

(9)-8  2.4.6- CO₂n-C₈H₁₇ 2,4,6- CO₂n-C₈H₁₇ trichlorophenylestertrichlorophenylester (9)-9  2.4.6- trichlorophenylester

2,4,6- trichlorophenylester

(9)-10 2.4.6- trichlorophenylester

2,4,6- trichlorophenylester

(9)-11 2,4,6- trichlorophenylester

2,4,6- trichlorophenylester

(9)-12 2 ,4,6- trichlorophenylester

2,4,6- trichlorophenylester

(9)-13 2,4,6- trichlorophenylester

2,4.6- trichlorophenylester

(9)-14 2,4.6- trichlorophenylester

2,4.6- trichlorophenylester

(9)-15 2,4- CO₂Me 2,4- CO₂Me dichlorophenylester dichlorophenylester(9)-16 4-chlorophenylester CO₂Me 4-chlorophenylester CO₂Me (9)-17phenylester CO₂Me phenylester CO₂Me (9)-18 4-nitrophenylester CO₂Me4-nitrophenylester CO₂Me (9)-19 2.6- CO₂Me 2,6- CO₂Medichlorophenylester dichlorophenylester (9)-20 2,4- CO₂Et 2.4- CO₂Etdichlorophenylester dichlorophenylester (9)-21 4-chlorophenylester

4-chlorophenylester

(9)-22 phenylester CO₂n-C₃H₇ phenylester CO₂n-C₃H₇ (9)-234-nitrophenylester CO₂n-C₄H₉ 4-nitrophenylester CO₂n-C₄H₉ (9)-24 2,6-CO₂n-C₅H₁₁ 2,6- CO₂n-C₅H₁₁ dichlorophenylester dichlorophenylester(9)-25 2,4- CO₂n-C₆H₁₃ 2,4- CO₂n-C₆H₁₃ dichlorophenylesterdichlorophenylester (9)-26 4-chlorophenylester

4-chlorophenylester

(9)-27 phenylester CO₂n-C₈H₁₇ phenylester CO₂n-C₈H₁₇ (9)-284-nitrophenylester

4-nitrophenylester

(9)-29 2,6- dichlorophenylester

2,6- dichlorophenylester

(9)-30 2,4- dichlorophenylester

2,4- dichlorophenylester

(9)-31 4-chlorophenylester

4-chlorophenylester

(9)-32 phenylester

phenylester

(9)-33 4-nitrophenylester

4-nitrophenylester

(9)-34 CO₂Et 2,4,6-trichlorophenylester CO₂Et 2,4,6-trichlorophenylester(9)-35 CO₂Et phenylester CO₂Et phenylester (9)-36 CO₂n-C₈H₁₇4-chlorophenylester CO₂n-C₈H₁₇ 4-chlorophenylester (9)-37 2.4,6-2,4,6-trichlorophenylester CO₂Et CO₂Et trichlorophenylester (9)-38 CO₂EtCO₂Et 2,4,6- 2,4,6-trichlorophenylester trichlorophenylester

Application

The cyclic imide compound obtained by the production method according toan embodiment of the present invention is used as a material for formingan organic semiconductor film of an electronic device such as an organicthin film transistor as described later.

Examples of such a device include organic thin film transistors thatcontrol the amount of current or voltage, organic photoelectricconversion elements that convert light energy into electric power (e.g.,solid image pickup elements for optical sensors, and solar cells forenergy conversion), organic thermoelectric conversion elements thatconvert thermal energy into electric power, organic electroluminescenceelements, (gas) sensors, organic rectifiers, organic inverters, andinformation recording elements.

Composition for Organic Thin Film Transistor

Next, a composition for organic thin film transistors will be described.

A composition for organic thin film transistors (also simply referred toas an “organic semiconductor composition” in this specification)includes a cyclic imide compound obtained by the production methodaccording to an embodiment of the present invention (hereafter alsoreferred to as a “particular cyclic imide compound”), and is used forforming an organic semiconductor film of an organic thin filmtransistor.

The particular cyclic imide compound included in the organicsemiconductor composition is as described above, and a single cyclicimide compound may be used or two or more cyclic imide compounds may beused in combination.

The content of the particular cyclic imide compound in the organicsemiconductor composition can be expressed as a content in the solidcontent excluding solvents described later. The content of theparticular cyclic imide compound relative to the total mass of the solidcontent in the organic semiconductor composition is preferably, forexample, in a preferred range of the content of the particular cyclicimide compound relative to the total mass of the organic semiconductorfilm described later.

Binder Polymer

The organic semiconductor composition may include a binder polymer. Fromthe viewpoint of obtaining an organic semiconductor film having highfilm quality, the organic semiconductor composition preferably includesa binder polymer.

The type of binder polymer is not particularly limited, and a publiclyknown binder polymer can be used. Examples of the binder polymer includeinsulating polymers such as polystyrene, poly(α-methylstyrene),polycarbonate, polyarylate, polyester, polyamide, polyimide,polyurethane, polysiloxane, polysulfone, polymethyl methacrylate,polymethyl acrylate, cellulose, polyethylene, and polypropylene, andcopolymers of the foregoing.

Other examples include rubbers such as ethylene-propylene rubbers,acrylonitrile-butadiene rubbers, hydrogenated nitrile rubbers,fluororubbers, perfluoroelastomers, tetrafluoroethylene-propylenecopolymers, ethylene-propylene-diene copolymers, styrene-butadienerubbers, polychloroprene, polyneoprene, butyl rubbers, methylphenylsilicone resins, methylphenylvinyl silicone resins, methylvinyl siliconeresins, fluorosilicone resins, acrylic rubbers, ethylene acrylicrubbers, chlorosulfonated polyethylene, chloropolyethylene,epichlorohydrin copolymers, polyisoprene-natural rubber copolymers,polyisoprene rubbers, styrene-isoprene block copolymers,polyester-urethane copolymers, polyether-urethane copolymers, polyetherester thermoplastic elastomers, and rubbers including polybutadienerubbers; and thermoplastic elastomer polymers.

Still other examples include photoconductive polymers such aspolyvinylcarbazole and polysilane; conductive polymers such aspolythiophene, polypyrrole, polyaniline, and polyparaphenylenevinylene;and semiconducting polymers described in Chemistry of Materials, 2014,26, 647.

In consideration of charge mobility, the binder polymer preferably has astructure including no polar group. Herein, the polar group refers to afunctional group having a heteroatom other than a carbon atom and ahydrogen atom. Polystyrene or poly(α-methylstyrene) is preferred as thebinder polymer because it has a structure including no polar group.Semiconducting polymers are also preferred.

The glass transition temperature of the binder polymer is notparticularly limited, and is appropriately set in accordance with theapplications. For example, in order to impart strong mechanical strengthto the organic semiconductor film, the glass transition temperature ispreferably increased. On the other hand, in order to impart flexibilityto the organic semiconductor film, the glass transition temperature ispreferably decreased.

The binder polymers may be used alone or in combination of two or more.

The content of the binder polymer in the organic semiconductorcomposition is not particularly limited. However, from the viewpoint offurther improving the carrier mobility and durability of the organicsemiconductor film of the organic thin film transistor, the content ofthe binder polymer relative to the total mass of the solid content inthe organic semiconductor composition is preferably within a preferredrange of the content of the binder polymer relative to the total mass ofthe organic semiconductor film described later.

The weight-average molecular weight of the binder polymer is notparticularly limited, but is preferably 1,000 to 10,000,000, morepreferably 3,000 to 5,000,000, and further preferably 5,000 to3,000,000. The weight-average molecular weight of the binder polymer canbe determined by gel permeation chromatography (GPC).

In the organic semiconductor composition, the particular cyclic imidecompound may be uniformly mixed with the binder polymer, or a part orall of the particular cyclic imide compound may be phase-separated fromthe binder polymer. From the viewpoint of coating easiness or coatinguniformity, the particular cyclic imide compound and the binder polymerare preferably uniformly mixed with each other at least at the time ofcoating.

Solvent

The organic semiconductor composition may include a solvent, andpreferably includes a solvent from the viewpoint of improving thecoatability thereof. Such a solvent is not particularly limited as longas the above-described compound can be dissolved or dispersed. Thesolvent is an inorganic solvent or an organic solvent, and preferably anorganic solvent. A single solvent may be used or two or more solventsmay be used in combination of two or more.

Non-limiting examples of the organic solvent include hydrocarbonsolvents such as hexane, octane, decane, toluene, xylene, mesitylene,ethylbenzene, diethylbenzene, amylbenzene, decalin, 1-methylnaphthalene,1-ethylnaphthalene, 1,6-dimethylnaphthalene, and tetralin; ketonesolvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone,cyclohexanone, acetophenone, propiophenone, and butyrophenone;halogenated hydrocarbon solvents such as dichloromethane, chloroform,tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane,chlorobenzene, 1,2-dichlorobenzene, trifluoromethyltoluene,1,2,4-trichlorobenzene, chlorotoluene, 1-chloronaphthalene, and1-fluoronaphthalene; heterocyclic solvents such as pyridine, picoline,quinoline, thiophene, 3-butylthiophene, and thieno[2,3-b]thiophene;halogenated heterocyclic solvents such as 2-chlorothiophene,3-chlorothiophene, 2,5-dichlorothiophene, 3,4-dichlorothiophene,2-bromothiophene, 3-bromothiophene, 2,3-dibromothiophene,2,4-dibromothiophene, 2,5-dibromothiophene, 3,4-dibromothiophene, and3,4-dichloro-1,2,5-thiadiazole; ester solvents such as ethyl acetate,butyl acetate, amyl acetate, 2-ethylhexyl acetate, γ-butyrolactone, andphenyl acetate; alcohol solvents such as methanol, propanol, butanol,pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve,and ethylene glycol; ether solvents such as dibutyl ether,tetrahydrofuran, dioxane, dimethoxyethane, anisole, ethoxybenzene,dimethoxybenzene, propoxybenzene, isopropoxybenzene, butoxybenzene,2-methylanisole, 3-methylanisole, 4-methylanisole, 4-ethylanisole,dimethylanisole (any of 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-, and 3,6-),and 1,4-benzodioxane; amide or imide solvents such asN,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone,1-methyl-2-imidazolidinone, and 1,3-dimethyl-2-imidazolidinone;sulfoxide solvents such as dimethylsulfoxide; phosphate solvents such astrimethyl phosphate; nitrile solvents such as acetonitrile andbenzonitrile; and nitro solvents such as nitromethane and nitrobenzene.

In particular, the organic solvent is preferably a hydrocarbon solvent,a ketone solvent, a halogenated hydrocarbon solvent, a heterocyclicsolvent, a halogenated heterocyclic solvent, or an ether solvent, morepreferably toluene, xylene, mesitylene, amylbenzene, tetralin,acetophenone, propiophenone, butyrophenone, dichlorobenzene, anisole,ethoxybenzene, propoxybenzene, isopropoxybenzene, butoxybenzene,dimethoxybenzene, chlorobenzene, dichlorobenzene, diethylbenzene,2-methylanisole, 3-methylanisole, 4-methylanisole, 1-fluoronaphthalene,1-chloronaphthalene, 3-chlorothiophene, or 2,5-dibromothiophene, andfurther preferably toluene, xylene, tetralin, acetophenone,propiophenone, butyrophenone, anisole, ethoxybenzene, propoxybenzene,butoxybenzene, 2-methylanisole, 3-methylanisole, 4-methylanisole,1-fluoronaphthalene, 1-chloronaphthalene, 3-chlorothiophene, or2,5-dibromothiophene.

The solvent included in the organic semiconductor composition ispreferably a solvent having a boiling point of 100° C. or higher fromthe viewpoint of ensuring the film quality and increasing the crystalsize of the above-described compound.

Examples of the solvent having a boiling point of 100° C. or higherinclude toluene, xylene, diethylbenzene, mesitylene, tetralin,acetophenone, propiophenone, butyrophenone, chlorobenzene,dichlorobenzene, anisole, dimethoxybenzene, ethoxybenzene,propoxybenzene, isopropoxybenzene, butoxybenzene, 2-methylanisole,3-methylanisole, 1-methylnaphthalene, 1-fluoronaphthalene,1-chloronaphthalene, and 4-methylanisole. In particular, the solvent ismore preferably toluene, xylene, diethylbenzene, chlorobenzene,dichlorobenzene, tetralin, acetophenone, propiophenone, butyrophenone,anisole, dimethoxybenzene, ethoxybenzene, propoxybenzene, butoxybenzene,2-methylanisole, 3-methylanisole, 1-methylnaphthalene,1-fluoronaphthalene, 1-chloronaphthalene, or 4-methylanisole.

From the viewpoints of environmental load and toxicity to humans, thesolvent having a boiling point of 100° C. or higher is preferably anon-halogen solvent (a solvent having no halogen atom in the molecule).

When the organic semiconductor composition includes a solvent, thecontent of the solvent is preferably 90 to 99.99 mass %, more preferably95 to 99.98 mass %, and further preferably 96 to 99.98 mass % relativeto the total mass of the organic semiconductor composition.

Other Components

The organic semiconductor composition may include components other thanthe particular cyclic imide compound, the binder polymer, and thesolvent. Such components are various additives.

Additives commonly used for organic semiconductor compositions can beused. More specifically, the additives are surfactants, antioxidants,crystallization controlling agents, and crystal alignment controllingagents. For the surfactants and the antioxidants, reference can be madeto paragraphs 0136 and 0137 in JP2015-195362A, the contents of which areincorporated herein by reference.

The content of the additives in the organic semiconductor composition isnot particularly limited. From the viewpoint of achieving good filmformability and further improving the carrier mobility and the heatresistance, the content of the additives relative to the total mass ofthe solid content in the organic semiconductor composition is preferablywithin a preferred range of the content of the additives relative to thetotal mass of the organic semiconductor film described later.

The viscosity of the organic semiconductor composition is preferably 10mPa-s or higher from the viewpoint of printability.

Preparation Method

The preparation method of the organic semiconductor composition is notparticularly limited, and an ordinary preparation method can beemployed. For example, an organic semiconductor composition can beprepared by adding a predetermined amount of each component to anorganic solvent and appropriately stirring the resulting mixture.

If necessary, heating may be performed during or after the stirring ofeach component. The heating temperature is not particularly limited andis determined within the range of, for example, 40° C. to 150° C. Whenthe solvent is used, the temperature is determined to be a temperaturethat is within the above range and is lower than the boiling point ofthe solvent.

Organic Thin Film Transistor

Next, an organic thin film transistor (hereafter also referred to as an“organic TFT”), which is a preferred form of the above-described organicsemiconductor device using the particular cyclic imide compound, will bedescribed.

The organic TFT includes an organic semiconductor film described later.Thus, the organic TFT exhibits high carrier mobility, and a decrease incarrier mobility over time is effectively suppressed even in theatmosphere, which achieves stable driving. Ambient temperature andhumidity in the atmosphere are not particularly limited as long as theyare the temperature and humidity in an operation environment of organicTFTs. The temperature is, for example, room temperature (20° C.) and thehumidity is, for example, 10 to 90 RH %.

The organic TFT is preferably used as an organic field effect transistor(FET), and more preferably used as an insulated gate FET in which a gateand a channel are insulated from each other.

The thickness of the organic TFT is not particularly limited. To providea thinner transistor, the thickness of the entire organic TFT ispreferably set to, for example, 0.1 to 0.5 μm.

The organic TFT has an organic semiconductor film (also referred to asan organic semiconductor layer or a semiconductor active layer)including a particular cyclic imide compound, and may further have asource electrode, a drain electrode, a gate electrode, and a gateinsulating film.

The organic TFT preferably has, over a substrate, a gate electrode, anorganic semiconductor film, a gate insulating film disposed between thegate electrode and the organic semiconductor film, and a sourceelectrode and a drain electrode that are disposed in contact with theorganic semiconductor film so as to be connected to each other throughthe organic semiconductor film. In this organic TFT, the organicsemiconductor film and the gate insulating film are disposed adjacent toeach other.

The structure of the organic TFT is not particularly limited as long asthe organic TFT includes the above-described layers. For example, theorganic TFT may have any of a bottom gate-bottom contact structure, atop gate-bottom contact structure, a bottom gate-top contact structure,and a top gate-top contact structure. The organic TFT preferably has abottom gate structure (bottom gate-bottom contact structure or bottomgate-top contact structure) in which a gate electrode is disposedbetween a substrate and an organic semiconductor film.

Hereafter, an example of the organic TFT will be described withreference to the attached drawings.

Bottom Gate-Bottom Contact Organic TFT

FIG. 1 is a sectional view schematically illustrating a structure of abottom gate-bottom contact organic TFT 10, which is an example of theorganic TFT.

As illustrated in FIG. 1 , the organic TFT 10 includes a substrate(base) 1, a gate electrode 2, a gate insulating film 3, a sourceelectrode 4A and a drain electrode 4B, an organic semiconductor film 5,and a sealing layer 6 in this order.

Hereafter, a substrate (base), a gate electrode, a gate insulating film,a source electrode, a drain electrode, an organic semiconductor film,and a sealing layer, and production methods thereof will be described.

Substrate

The substrate serves to support the gate electrode, the sourceelectrode, the drain electrode, and other layers.

The type of substrate is not particularly limited, and is, for example,a plastic substrate, a silicon substrate, a glass substrate, or aceramic substrate. Among them, a glass substrate or a plastic substrateis preferable from the viewpoint of applicability to devices and cost.

The thickness of the substrate is not particularly limited. The upperlimit of the thickness of the substrate is preferably 10 mm or less,more preferably 2 mm or less, and further preferably 1.5 mm or less. Thelower limit of the thickness of the substrate is preferably 0.01 mm ormore and more preferably 0.05 mm or more.

Gate Electrode

An electrode commonly used as a gate electrode of an organic TFT can beapplied as the gate electrode without particular limitation.

Non-limiting examples of the material (electrode material) for formingthe gate electrode include metals such as gold, silver, aluminum,copper, chromium, nickel, cobalt, titanium, platinum, magnesium,calcium, barium, and sodium; conductive oxides such as InO₂, SnO₂, andindium tin oxide (ITO); conductive polymers such as polyaniline,polypyrrole, polythiophene, polyacetylene, and polydiacetylene;semiconductors such as silicon, germanium, and gallium arsenide; andcarbon materials such as fullerene, carbon nanotube, and graphite. Amongthese, the metal is preferable, and silver or aluminum is morepreferable.

The thickness of the gate electrode is not particularly limited, but ispreferably 20 to 200 nm.

The gate electrode may function as the substrate, and in this case, thesubstrate may be omitted.

A method for forming the gate electrode is not particularly limited.Examples of the method include a method in which the above-describedelectrode material is subjected to vacuum deposition (hereafter alsosimply referred to as “deposition”) or sputtering on a substrate and amethod in which an electrode-forming composition including theabove-described electrode material is applied or printed. When the gateelectrode is patterned, examples of the patterning method includeprinting methods such as inkjet printing, screen printing, offsetprinting, and relief printing (flexographic printing), aphotolithography method, and a mask vapor deposition method.

Gate Insulating Film

The gate insulating film is not particularly limited as long as it is alayer having insulating properties, and may have a single-layerstructure or a multilayer structure.

Non-limiting examples of the material for forming the gate insulatingfilm include polymers such as polymethyl methacrylate, polystyrene,polyvinylphenol, melamine resin, polyimide, polycarbonate, polyester,polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfone,polybenzoxazole, polysilsesquioxane, epoxy resin, and phenolic resin;inorganic oxides such as silicon dioxide, aluminum oxide, and titaniumoxide; and nitrides such as silicon nitride. Among them, the polymer ispreferable in view of compatibility with the organic semiconductor film.The inorganic oxide is preferable and silicon dioxide is more preferablein view of uniformity of the film.

These materials may be used alone or in combination of two or more.

The thickness of the gate insulating film is not particularly limited,but is preferably 100 to 1000 nm.

A method for forming the gate insulating film is not particularlylimited. Examples of the method include a method in which a gateinsulating film-forming composition including the above-describedmaterial is applied onto the substrate on which the gate electrode hasbeen formed and a method in which the above-described material issubjected to vapor deposition or sputtering.

Source Electrode and Drain Electrode

In the organic TFT, the source electrode is an electrode into which acurrent flows from the outside through a wiring line. The drainelectrode is an electrode that sends a current to the outside through awiring line.

The material for forming the source electrode and the drain electrodemay be the same as the electrode material for forming the gateelectrode. Among them, the metal is preferable, and gold or silver ismore preferable.

The thickness of each of the source electrode and the drain electrode isnot particularly limited, but is preferably 1 nm or more and morepreferably 10 nm or more. The upper limit of the thicknesses of thesource electrode and the drain electrode is preferably 500 nm or lessand more preferably 300 nm or less.

The distance (gate length L) between the source electrode and the drainelectrode can be appropriately determined, but is preferably 200 μm orless and more preferably 100 μm or less. The gate width W can beappropriately determined, but is preferably 5000 μm or less and morepreferably 1000 μm or less. The ratio of the gate width W to the gatelength L is not particularly limited. For example, the ratio W/L ispreferably 10 or more and more preferably 20 or more.

A method for forming the source electrode and the drain electrode is notparticularly limited. Examples of the method include a method in whichthe electrode material is subjected to vacuum deposition or sputteringon a substrate on which the gate electrode and the gate insulating filmhave been formed and a method in which an electrode-forming compositionis applied or printed. The patterning method employed when the sourceelectrode and the drain electrode are patterned is the same as thepatterning method of the gate electrode.

Organic Semiconductor Film

An organic semiconductor film including a particular cyclic imidecompound is used as an organic semiconductor film in an organic TFT. Thenumber of types of particular cyclic imide compounds included in theorganic semiconductor film may be one or may be two or more.

When the organic semiconductor film includes a particular cyclic imidecompound, the carrier mobility of the organic semiconductor film can beimproved, and the high carrier mobility can be maintained even if theorganic semiconductor film is used or stored (left) in the atmosphere.The reason for this is unclear, but it is believed that the orbitalenergy of the lowest unoccupied molecular orbital of the particularcyclic imide compound is low.

The content of the particular cyclic imide compound in the organicsemiconductor film is not particularly limited and can be appropriatelyset. For example, the content of the particular cyclic imide compoundrelative to the total mass of the organic semiconductor film ispreferably 10 mass % or more, more preferably 30 mass % or more, andfurther preferably 50 mass % or more. The upper limit of the content isnot particularly limited, and the content of the particular cyclic imidecompound relative to the total mass of the organic semiconductor filmmay be 100 mass %. In the case where the organic semiconductor filmincludes a binder polymer or other components, the upper limit of thecontent of the particular cyclic imide compound relative to the totalmass of the organic semiconductor film is preferably 90 mass % or lessand more preferably 80 mass % or less.

The organic semiconductor film may include the above-described binderpolymer in addition to the particular cyclic imide compound. The binderpolymers may be used alone or in combination of two or more.

In the organic semiconductor film, the state of the particular cyclicimide compound and the binder polymer is not particularly limited. Fromthe viewpoint of carrier mobility, the particular cyclic imide compoundand the binder polymer are preferably phase-separated from each other inthe film thickness direction.

The content of the binder polymer in the organic semiconductor film isnot particularly limited and can be appropriately set. In the case wherethe organic semiconductor film includes a binder polymer, the content ofthe binder polymer relative to the total mass of the organicsemiconductor film is preferably 90 mass % or less and more preferably70 mass % or less. The lower limit of the content is not particularlylimited, and the content of the binder polymer relative to the totalmass of the organic semiconductor film can be set to 0 mass % or more,and is preferably 10 mass % or more and more preferably 20 mass % ormore.

The organic semiconductor film may include the above-described additivein addition to the particular cyclic imide compound. The additives maybe used alone or in combination of two or more.

In the case where the organic semiconductor film includes an additive,the content of the additive relative to the total mass of the organicsemiconductor film is preferably 10 mass % or less, more preferably 5mass % or less, and further preferably 1 mass % or less.

The thickness of the organic semiconductor film is appropriatelydetermined in accordance with the organic TFT to be applied, but ispreferably 10 to 500 nm and more preferably 20 to 200 nm.

This organic semiconductor film can be formed by applying theabove-described organic semiconductor composition. The details of amethod for forming the organic semiconductor film will be describedlater.

The applications of the organic semiconductor film including aparticular cyclic imide compound are not limited to organicsemiconductor films for organic TFTs. The organic semiconductor film canbe used as an organic semiconductor film included in each of the organicsemiconductor devices described above.

Sealing Layer

Since the organic TFT including the organic semiconductor film is stablydriven even in the atmosphere, it is not necessary to seal the entireorganic TFT and block any of the air (oxygen gas) and moisture. However,for the purpose of stable driving for a longer time, the entire organicTFT may be sealed with a metal sealing can or a sealing layer may beformed using a sealing agent.

For the sealing layer, a sealing agent (sealing layer-formingcomposition) commonly used for organic TFTs can be used. Examples of thesealing agent include inorganic materials such as glass and siliconnitride, polymer materials such as parylene, and low-molecular-weightmaterials.

The sealing layer can be formed by a typical method such as coating anddrying using the sealing agent.

The thickness of the sealing layer is not particularly limited, but ispreferably 0.2 to 10 μm.

Bottom Gate-Top Contact Organic TFT

FIG. 2 is a sectional view schematically illustrating a structure of abottom gate-top contact organic TFT 20, which is an example of theorganic TFT.

As illustrated in FIG. 2 , the organic TFT 20 includes a substrate 1, agate electrode 2, a gate insulating film 3, an organic semiconductorfilm 5, a source electrode 4A and a drain electrode 4B, and a sealinglayer 6 in this order.

The organic TFT 20 is the same as the organic TFT 10, except that thelayer structure (lamination form) is different. Therefore, thesubstrate, the gate electrode, the gate insulating film, the sourceelectrode, the drain electrode, the organic semiconductor film, and thesealing layer are the same as those in the bottom gate-bottom contactorganic TFT described above, and thus the description thereof isomitted.

Method for Producing Organic TFT

A method for producing an organic TFT is not particularly limited aslong as the method has a step of applying an organic semiconductorcomposition onto a substrate to form an organic semiconductor film.

The gate electrode, the gate insulating film, the source electrode, thedrain electrode, and the sealing layer can each be formed or depositedby the above methods.

Hereafter, a step of forming an organic semiconductor film will bedescribed.

In this step, the above-described organic semiconductor composition isused.

In the present invention, the phrase “applying an organic semiconductorcomposition onto a substrate” covers not only a form in which an organicsemiconductor composition is directly applied onto a substrate, but alsoa form in which an organic semiconductor composition is applied above asubstrate, that is, on another layer disposed on the substrate. Theother layer (a layer that is in contact with the organic semiconductorfilm and serves as a base of the organic semiconductor film) onto whichthe organic semiconductor composition is applied is naturally determinedin accordance with the structure of the organic TFT. For example, whenthe organic TFT is a bottom gate organic TFT, the organic semiconductorcomposition is applied onto at least a surface of the gate insulatingfilm.

When the organic semiconductor film is formed, the substrate may beheated or cooled. By changing the temperature of the substrate, the filmquality or the packing of the particular cyclic imide compound in thefilm can be controlled.

The temperature of the substrate is not particularly limited. Forexample, the temperature of the substrate is preferably set within arange of 0° C. to 200° C., more preferably within a range of 15° C. to100° C., and further preferably within a range of 20° C. to 95° C.

The method for forming the organic semiconductor film is notparticularly limited as long as the organic semiconductor film includingthe particular cyclic imide compound can be formed. The method is, forexample, a vacuum process or a solution process, and is preferably asolution process.

Examples of the vacuum process include physical vapor deposition methodssuch as vacuum deposition, sputtering, ion plating, and molecular beamepitaxy (MBE); and chemical vapor deposition (CVD) methods such asplasma polymerization. In particular, the vacuum deposition ispreferable.

In the solution process, the above-described organic semiconductorcomposition is preferably used.

The particular cyclic imide compound is stable even in the atmosphere asdescribed above. Thus, the solution process can be performed in theatmosphere, and the organic semiconductor composition can be applied ina large area.

A common method for applying an organic semiconductor composition in thesolution process can be employed. Examples of the method include coatingmethods such as a drop casting method, a casting method, a dip coatingmethod, a die coater method, a roll coater method, a bar coater method,and a spin coating method; various printing methods such as an inkjetmethod, a screen printing method, a gravure printing method, aflexographic printing method, an offset printing method, and amicrocontact printing method; and a Langmuir-Blodgett (LB) method. Amongthem, a drop casting method, a casting method, a spin coating method, aninkjet method, a gravure printing method, a flexographic printingmethod, an offset printing method, or a microcontact printing method ispreferable.

The method for applying an organic semiconductor composition in apreferred embodiment of the solution process described later ispreferably an inkjet method, a gravure printing method, a flexographicprinting method, an offset printing method, or a microcontact printingmethod and more preferably a flexographic printing method, amicrocontact printing method, or an inkjet method.

In the solution process, it is preferable to dry the organicsemiconductor composition applied onto the substrate, and it is morepreferable to gradually dry the organic semiconductor composition. Bydrying the organic semiconductor composition applied onto the substrate,a crystal of the particular cyclic imide compound can be precipitated toform an organic semiconductor film.

The method for drying an organic semiconductor composition is preferablynatural drying, or heat drying on a heated substrate followed by dryingunder reduced pressure from the viewpoint of film quality. Thetemperature of the substrate during natural drying or heat drying ispreferably 20° C. to 100° C. and more preferably 50° C. to 80° C. Thetime of natural drying or heat drying is preferably 0.5 to 20 hours andmore preferably 1 to 10 hours.

The temperature of the substrate during drying under reduced pressure ispreferably 20° C. to 100° C. and more preferably 40° C. to 80° C. Thetime of drying under reduced pressure is preferably 1 to 20 hours andmore preferably 2 to 10 hours. The pressure during drying under reducedpressure is preferably 10⁻⁶ to 10⁴ Pa and more preferably 10⁻⁵ to 10⁻³Pa.

The thus-dried organic semiconductor composition may be shaped into apredetermined shape or a pattern shape as necessary.

Embodiment of Solution Process

Hereafter, the preferred embodiment of the solution process will bedescribed with reference to the attached drawings, but the solutionprocess is not limited to the following embodiment.

An embodiment of the solution process is a method in which an organicsemiconductor composition (hereafter also referred to as a “coatingliquid”) is dropped (applied) onto a part of a surface of a substrate soas to be in contact with a substrate and a member disposed on thesubstrate (hereafter also simply referred to as a “member”), and thenthe dropped coating liquid is dried. The substrate and the member usedin this embodiment will be described later.

In this embodiment, the member is kept in contact with the substrate, orthe member is not fixed to the substrate and is kept at a constantdistance from the substrate.

As long as the substrate and the member keep the above-described state,the relative positional relationship between the substrate and themember may be fixed or changed when the coating liquid is dropped ordried. In terms of production efficiency, the relative positionalrelationship between the substrate and the member is preferably changedby moving the member with respect to the substrate. In terms of the filmquality and crystal size of the organic semiconductor film to beobtained, the relative positional relationship between the substrate andthe member is preferably fixed by making the member stand still withrespect to the substrate.

The dropping method of the coating liquid in this embodiment is notparticularly limited. From the viewpoint that the thickness of the filmof the coating liquid on the substrate tends to be thin and drying tendsto progress from the end portion of the film of the coating liquid, whenthe coating liquid is dropped, it is preferable that a single droplet ofthe coating liquid is dropped, or a single droplet is dropped at a timewhen two or more droplets are dropped. When the coating liquid isdropped, the volume of a single droplet of the coating liquid ispreferably 0.01 to 0.2 mL and more preferably 0.02 to 0.1 mL.

By dropping the coating liquid onto a part of the surface of thesubstrate so as to be in contact with both the substrate and the member,the thickness of the end portion of the film of the coating liquid canbe decreased.

The contact angle (25° C.) of the coating liquid with respect to thesubstrate is not particularly limited, but is preferably 0° to 90° andmore preferably 10° to 20°. The contact angle of the coating liquid withrespect to the substrate is determined by measuring the angle betweenthe liquid droplet and the substrate one second after the coating liquid(solid content: 0.1 mass %, solvent: anisole) is dropped. Specifically,the liquid volume is set to 1.0 μL or more, and a static contact angleis measured by a droplet method using a Teflon (registered trademark)needle. This is performed a plurality of times (normally five times) ondifferent substrates obtained in the same manner, and the average valueis calculated and used as a contact angle.

The coating liquid preferably forms a meniscus on the member, and morepreferably forms a concave meniscus on the member in terms of filmquality.

Hereafter, a method for applying the coating liquid while the distancebetween the substrate and the member is kept constant in this embodimentwill be described with reference to FIGS. 3A to 3C. FIGS. 3A to 3C areschematic views illustrating an example of the method for forming anorganic semiconductor film of an organic TFT.

In this method, first, a substrate 42 and a member 43 are disposed atpredetermined positions. Specifically, before a coating liquid 41 isdropped onto the substrate, the substrate 42 and the member 43 aredisposed at positions illustrated in FIG. 3A. At this time, the distancebetween the substrate 42 and the member 43 that is not in contact withthe substrate 42 is kept constant. The distance between the substrate 42and the member 43 cannot be unconditionally determined because thedistance varies depending on, for example, the coating amount andviscosity of the coating liquid, but can be appropriately set.

Next, as illustrated in FIG. 3B, the coating liquid 41 is dropped onto apart of the surface of the substrate 42 (the vicinity of a portion wherethe substrate 42 and the member 43 face each other) so as to be incontact with both the substrate 42 and the member 43.

Then, the coating liquid 41 is dried while the relative positionalrelationship between the substrate 42 and the member 43 is fixed (FIG.3C). The drying method is not particularly limited, but theabove-described drying method of the organic semiconductor compositionis preferred. Thus, the coating liquid 41 is dried from both endportions (end edges) having a small film thickness toward the inside onthe substrate 42, and the particular cyclic imide compound iscrystallized. As a result, the particular cyclic imide compound can bedisposed at a predetermined position as a crystal having a large size.

After the coating liquid 41 is dried, the member 43 is separated fromthe substrate 42 by, for example, pulling up the member 43 in adirection perpendicular to the main surface of the substrate 42. Thiscan achieve formation of an organic semiconductor film having high filmquality without leaving a trace of the member 43 in the formed crystal.

In this manner, an organic semiconductor film made of a crystal of theparticular cyclic imide compound can be formed.

Hereafter, a method for applying the coating liquid while the substrateand the member are in contact with each other in this embodiment will bedescribed with reference to FIGS. 4A to 4D. FIGS. 4A to 4D are schematicviews for describing another example of the method for forming anorganic semiconductor film of an organic TFT.

In this method, first, the substrate 42 and the member 43 are disposedin contact with each other. Specifically, before a coating liquid 41 isdropped onto the substrate 42, the substrate 42 and the member 43 aredisposed at positions illustrated in FIG. 4A.

Next, as illustrated in FIGS. 4B1 and 4B2, the coating liquid 41 isdropped onto a part of the surface of the substrate 42 (the vicinity ofa contact portion between the substrate 42 and the member 43) so as tobe in contact with both the substrate 42 and the member 43. At thistime, as illustrated in FIG. 4B2, the coating liquid 41 preferablysurrounds the contact portion between the substrate 42 and the member43. FIG. 4B1 is a front view of the substrate onto which the coatingliquid has been applied, and FIG. 4B2 is a plan view of the substrateonto which the coating liquid has been applied. Three-dimensionalcoordinates (X, Y, Z) are shown in FIGS. 4B1 and 4B2.

Then, the coating liquid 41 is dried preferably as described above whilethe relative positional relationship between the substrate 42 and themember 43 is fixed (FIG. 4C). The drying method is not particularlylimited, but the above-described drying method of the organicsemiconductor composition is preferred. Thus, the coating liquid 41 isdried from end edges having a small film thickness toward the inside onthe substrate 42, and the particular cyclic imide compound iscrystallized. As a result, the particular cyclic imide compound can bedisposed at a predetermined position as a crystal having a large size.

After the coating liquid 41 is dried, the member 43 is separated fromthe substrate 42 by, for example, pulling up the member 43 in adirection perpendicular to the main surface of the substrate 42.Consequently, as illustrated in FIG. 4D, an organic semiconductor film 5having high film quality and made of a crystal of the particular cyclicimide compound can be formed without leaving a trace of the member 43 inthe crystal of the particular cyclic imide compound.

The method for applying a coating liquid while the substrate 42 and themember 43 are in contact with each other is preferred to the method forapplying a coating liquid while the distance between the substrate 42and the member 43 is kept constant in terms of film quality, in terms ofnot requiring a mechanism for holding the member 43, and in terms ofbeing able to keep the distance (contact state) between the substrate 42and the member 43.

Hereafter, another method for applying the coating liquid while thesubstrate and the member are in contact with each other in thisembodiment will be described with reference to FIGS. 5A to 5C. FIGS. 5Ato 5C are schematic views for describing another example of the methodfor forming an organic semiconductor film of an organic TFT.

This method is different from the method illustrated in FIGS. 4A to 4Din that crystallization of the particular cyclic imide compound isfacilitated by moving the member 43 with respect to the substrate 42while the distance between the substrate 42 and the member 43 is keptconstant.

In this method, first, the substrate 42 and the member 43 are disposedin contact with each other. Specifically, before a coating liquid 41 isdropped onto the substrate 42, the substrate 42 and the member 43 aredisposed at positions illustrated in FIG. 5A.

Next, as illustrated in FIG. 5B, the coating liquid 41 is dropped onto apart of the surface of the substrate 42 (the vicinity of a contactportion between the substrate 42 and the member 43) so as to be incontact with both the substrate 42 and the member 43. At this time, asillustrated in FIG. 4B2, the coating liquid 41 preferably surrounds thecontact portion between the substrate 42 and the member 43.

Then, the coating liquid 41 is dried by moving the member 43 withrespect to the substrate 42 while the distance between the substrate 42and the member 43 is kept constant. For example, the member 43 is movedwith respect to the substrate 42 in a direction indicated by an arrow(negative X-axis direction) in FIG. 5C. The drying of the coating liquid41 progresses from the end portion (the side in a positive X-axisdirection) on the side opposite to the moving destination of the member43 toward the moving destination (the side in a negative X-axisdirection), and the particular cyclic imide compound is crystallized. Asa result, the particular cyclic imide compound can be disposed at apredetermined position as a crystal having a large size.

After the coating liquid 41 is dried, the member 43 is separated fromthe substrate 42 by, for example, pulling up the member 43 in adirection perpendicular to the main surface of the substrate 42.Consequently, an organic semiconductor film having high film quality andmade of the particular cyclic imide compound can be formed withoutleaving a trace of the member 43 in the crystal of the particular cyclicimide compound.

The substrate 42 used in this embodiment corresponds to a substrate ofan organic TFT, and is preferably a substrate on which a gate insulatingfilm is formed.

The member 43 used in this embodiment is not particularly limited, butthe material for the member 43 is preferably an inorganic material (morepreferably glass, quartz, or silicon) or a plastic (more preferablyTeflon (registered trademark), polyethylene, or polypropylene), and morepreferably glass.

The shape of the member 43 used in this embodiment is not particularlylimited as long as it has a smooth surface facing the substrate 42, butis preferably a rectangular parallelepiped.

FIG. 6 is a schematic view illustrating an example of the substrate 42and the member 43 used in this embodiment. In FIG. 6 , the shape of themember 43 is a rectangular parallelepiped, d and w represent the lengthsof one side and the other side of a surface of the member 43 facing thesubstrate 42, respectively, and h represents the height of the member43.

The size of the member 43 used in this embodiment is not particularlylimited. When the member 43 has a rectangular parallelepiped shape asillustrated in FIG. 6 , the lower limit of the lengths of one side andthe other side (d and w in FIG. 6 ) of a surface of the member 43 facingthe substrate 42 is preferably 0.1% or more, more preferably 1% or more,further preferably 10% or more, and particularly preferably 20% or morerelative to the length of one side of a main surface (a surface ontowhich the coating liquid is applied) of the substrate 42. The upperlimit of the lengths of the one side and the other side is preferably80% or less, more preferably 70% or less, and further preferably 50% orless relative to the length of one side of the main surface of thesubstrate 42. The height (h in FIG. 6 ) of the member 43 is preferably 1to 50 mm and more preferably 5 to 20 mm. Furthermore, the ratio h/d ofthe height h to the length d of the member 43 is preferably 0.01 to 10and more preferably 0.1 to 5 in terms of the arrangement stability ofthe member 43. The ratio w/d of the length w to the length d of themember 43 is preferably 1 to 1000 and more preferably 5 to 100 becausethe particular cyclic imide compound can be crystallized in a wide area.

In this manner, an organic semiconductor film can be formed byprecipitating a crystal of the particular cyclic imide compound. Whethera crystal of the particular cyclic imide compound is precipitated can bechecked by observing the organic semiconductor film using a polarizingmicroscope (trade name: Eclipse LV100N POL (diascopic/episcopicillumination type), manufactured by Nikon Corporation, ocular lens: 10times, objective lens: 5 to 20 times).

Application of Organic TFT

The applications of the above-described organic TFT are not particularlylimited. The organic TFT can be used for, for example, electronic paper,display devices, sensors, and electronic tags.

EXAMPLES

Hereafter, the present invention will be described in further detailbased on Examples. Materials, used amounts, ratios, processing contents,processing procedures, and the like shown in Examples below can beappropriately changed without departing from the spirit of the presentinvention. Therefore, the scope of the present invention should not beconstrued as being limited by Examples below.

Example 1: Synthesis of Compound (1-1)

Purification of Compound (1-3)

A compound (1-3) was purified by recrystallization from hexane-ethylacetate. Synthesis of composition (raw material composition) includingcompound (1-4)

Into a glass reaction vessel equipped with a pressure-resistant balloon,20 g (37.9 mmol) of a compound (1-2), 200 mL of toluene, 0.851 g (3.79mmol) of palladium acetate, 4.39 g (7.58 mmol) of xantphos, and 51.0 g(227 mmol) of the compound (1-3) were charged, and the reaction vesselwas nitrogen-purged. After 37.0 mL (265 mmol) of triethylamine was addeddropwise with a syringe, stirring was performed at 75° C. to 85° C. forseven hours. After cooling to room temperature, the precipitated solidwas filtered. The obtained solid was dispersed in methanol, stirred atroom temperature for 30 minutes, and then collected by filtration. Thefilter residue was dissolved in chloroform, and silica gel was addedthereto, and filtration was performed. The filtrate was concentratedunder reduced pressure and recrystallized from o-dichlorobenzene toobtain 23.2 g (28.4 mmol, yield 69.6%) of a composition including acompound (1-4). The content of the compound (1-4) in the obtainedcomposition was 98.6 mass % relative to the total solid content of thecomposition, and the content of the compound (1-4′) was 0.1 mass % orless relative to the total solid content of the composition.

The “raw material composition” in the column of Example 1 in Table 5below refers to a composition including the compound (1-4) obtainedherein.

Synthesis of Compound (1-1)

Into a glass reaction vessel, 1.00 g (1.22 mmol) of a compositionincluding the compound (1-4), 40 mL of o-dichlorobenzene, and 593 mg(4.89 mmol) of phenethylamine were charged, and stirring was performedat 150° C. for 2 hours. After cooling to room temperature, methanol wasadded and the solid was collected by filtration. The obtained solid wasdried in vacuum and then purified by sublimation to obtain 466 mg (0.776mmol, yield 63.6%) of a compound (1-1).

Example 2: Synthesis of Compound (1-1) Production of Composition (RawMaterial Composition) Including Compound (1-4)

A composition including the compound (1-4) was obtained in the samemanner as in Example 1, except that the compound (1-3) was not purifiedby recrystallization. The content of the compound (1-4) in the obtainedcomposition was 94.9 mass % relative to the total solid content of thecomposition, and the content of the compound (1-4′) was 3.0 mass %relative to the total solid content of the composition.

The “raw material composition” in the column of Example 2 in Table 5below refers to a composition including the compound (1-4) obtainedherein.

Synthesis of Compound (1-1)

By the same method as in Example 1, 451 mg (0.751 mmol, yield 61.5%) ofa compound (1-1) was obtained.

Example 3: Synthesis of Compound (3-1)

Synthesis of Compound (3-1)

A compound (3-1) was obtained in an amount of 452 mg (0.733 mmol, yield60.1%) in the same manner as in Example 1, except that 631 mg (4.89mmol) of n-octylamine was used instead of phenethylamine.

Example 4: Production of Compound (4-1)

A compound (4-1) was obtained in an amount of 480 mg (0.764 mmol, yield62.6%) in the same manner as in Example 1, except that 661 mg (4.89mmol) of 3-phenylpropylamine was used instead of phenethylamine.

Example 5: Synthesis of Compound (1-1)

Production of Compound (1-1)

A compound (1-1) was obtained in an amount of 447 mg (0.745 mmol, yield61.1%) in the same manner as in Example 1, except that 745 mg (1.22mmol) of a composition including a compound (5-2) below was used insteadof the composition including the compound (1-4).

In the composition including the compound (5-2), the content of thecompound (5-2) was 98.1 mass % relative to the total solid content ofthe composition including the compound (5-2), and the content of thecompound (5-2′) was 0.1 mass % or less relative to the total solidcontent of the composition including the compound (5-2).

The “raw material composition” in the column of Example 5 in Table 5below refers to a composition including the compound (5-2).

Example 6: Synthesis of Compound (1-1)

Synthesis of Compound (1-1)

A compound (1-1) was obtained in an amount of 462 mg (0.770 mmol, yield63.1%) in the same manner as in Example 1, except that 829 mg (1.22mmol) of a composition including a compound (6-2) was used instead ofthe composition including the compound (1-4).

In the composition including the compound (6-2), the content of thecompound (6-2) was 98.2 mass % relative to the total solid content ofthe composition including the compound (6-2), and the content of thecompound (6-2′) was 0.1 mass % or less relative to the total solidcontent of the composition including the compound (6-2).

The “raw material composition” in the column of Example 6 in Table 5below refers to a composition including the compound (6-2).

Example 7: Synthesis of Compound (1-1) Purification of Compound (1-3)

The compound (1-3) was washed with cold hexane.

Synthesis of Composition (Raw Material Composition) Including Compound(1-4)

A composition including the compound (1-4) was obtained in the samemanner as in Example 1, except that the compound (1-3) was used. Thecontent of the compound (1-4) in the obtained composition was 97.8 mass% relative to the total solid content of the composition, and thecontent of the compound (1-4′) was 1.0 mass % relative to the totalsolid content of the composition.

The “raw material composition” in the column of Example 7 in Table 5below refers to a composition including the compound (1-4) obtainedherein.

Synthesis of Compound (1-1)

By the same method as in Example 1, 445 mg (0.741 mmol, yield 60.7%) ofa compound (1-1) was obtained.

Comparative Example 1: Synthesis of Compound (1-1)

Synthesis of Compound (C1-1)

Into a glass reaction vessel, 410 mg (0.502 mmol) of a compound (1-4),477 mg (2.51 mmol) of p-toluenesulfonic acid monohydrate, and 40 mL ofo-dichlorobenzene were charged, and stirring was performed at 120° C.for 12 hours. After the reaction solution was concentrated under reducedpressure, the solid was dispersed in hexane and collected by filtration.The resulting solid was dispersed in ethyl acetate, then collected byfiltration, and washed with ethyl acetate to obtain 95 mg (0.240 mmol,yield 47.8%) of a compound (C1-1).

Synthesis of Compound (1-1)

Into a glass reaction vessel, 500 mg (1.27 mmol) of the compound (C1-1),615 mg (5.07 mmol) of 2-phenylethylamine, and 20 mL of o-dichlorobenzenewere charged, and stirring was performed at 150° C. for 3 hours. Aftercooling with water, 40 mL of methanol was added, and filtration wasperformed for collection. The obtained solid was dried under reducedpressure and then purified by sublimation to obtain 375 mg (0.624 mmol,yield 49.1%) of a compound (1-1).

The yield of the compound (1-1), which was a final target compound,relative to the compound (1-4) was 23.5%.

Comparative Example 2: Production of Compound (1-1)

A compound (1-1) was obtained in an amount of 611 mg (1.02 mmol, yield80.1%) in the same manner as in Comparative Example 1, except thatpurification by sublimation was not performed.

The yield of the compound (1-1), which was a final target compound,relative to the compound (1-4) was 38.3%.

Evaluation Analysis of Purity by Liquid Chromatography

The cyclic imide compounds finally obtained by the production methods inExamples and Comparative Examples were analyzed by liquid chromatographyunder the following conditions and evaluated based on the followingcriteria.

Column: Tosoh TSKgel Silica-150 (particle size: 5 μm, inner diameter:4.6 mm, length: 25 cm)

Eluant: chloroform/hexafluoroisopropanol=9/1

Flow rate: 0.8 mL/min

Injection volume: 10 μL

Column temperature: 25° C.

Detection wavelength: 254 nm

Sample: 50 w/v ppm (solvent: chloroform/hexafluoroisopropanol=4/1)

Evaluation Criteria

A: The area percentage of the target is 99% or more.

B: The area percentage of the target is 97.5% or more and less than 99%.

C: The area percentage of the target is 95% or more and less than 97.5%.

D: The area percentage of the target is less than 95%.

Production and Evaluation of Organic Thin Film Transistor Production ofOrganic Thin Film Transistor

A substrate (size: 25 mm×25 mm) in which a SiO₂ thermally oxidized film(thickness: 200 nm) was formed on a surface of an n-type siliconsubstrate (thickness: 0.4 mm, corresponding to the substrate 1 providedwith the gate electrode 2) 1 was provided as a substrate for measuringFET characteristics. The surface of the thermally oxidized film (gateinsulating film 3) of the substrate was cleaned with ultraviolet(UV)-ozone and then treated with β-phenethyltrimethoxysilane.

A glass member having a size of 10 mm in length×2 mm in width×5 mm inheight was provided. The member serving as a member 43 illustrated inFIGS. 4A to 4D was disposed at a central portion of the surface of thesubstrate 1 treated with β-phenethyltrimethoxysilane as illustrated inFIG. 4A while the member was in contact with the treated surface.

Then, as illustrated in FIG. 4A, a single droplet (about 0.05 mL) of a1-methylnaphthalene solution (0.03 mass %) of the compound obtained bythe production method in each of Examples and Comparative Examples wasdropped onto the substrate 1 (indicated by reference numeral 42 in FIGS.4A to 4D) heated to 100° C. near the contact portion between thesubstrate 42 and the member 43 from the side of the member 43 using apipet so as to be in contact with the substrate 42 and the member 43. Asillustrated in FIGS. 4B1 and 4B2, the coating liquid surrounded thecontact portion and formed a concave meniscus at the interface with themember 43. The contact angle (25° C.) of the coating liquid 41 relativeto the substrate 42 was 10°.

As illustrated in FIG. 4C, the coating liquid 41 was dried at 150° C.while the substrate 42 and the member 43 were in contact with each otherand the positional relationship between the substrate 42 and the member43 was not changed. Then, the resulting film was dried under a reducedpressure of 10⁻³ Pa at 60° C. for 8 hours to produce a crystal film ofan organic semiconductor film. Subsequently, the member 43 was pulled upin a direction perpendicular to the substrate 42 to separate the member43 from the substrate 42. Thus, a ring-shaped organic semiconductor film5 having the above-described uniform thickness (thickness: 10 to 50 nm)was formed as illustrated in FIG. 4D.

The obtained organic semiconductor film 5 was observed with a polarizingmicroscope Eclipse LV100N POL (diascopic/episcopic illumination type,manufactured by Nikon Corporation, ocular lens: 10 times, objectivelens: 5 to 20 times). As a result, the crystal of the above compound wasprecipitated.

A mask having a predetermined opening was disposed on the obtainedorganic semiconductor film 5, and vapor deposition was performed usinggold to form a source electrode 4A and a drain electrode 4B (each havinga thickness of 40 nm, a gate width W of 2 mm, a gate length L of 50 μm,and a ratio W/L of 40). In this manner, an organic thin film transistorfor measuring FET characteristics was produced.

For the evaluation described later, ten organic thin film transistorswere produced using the compound obtained by the production method ineach of Examples and Comparative Examples.

Evaluation of Organic Thin Film Transistor 1. Method for MeasuringCarrier Mobility μ

The carrier mobility of each of the produced organic thin filmtransistors was measured at a normal atmospheric pressure of 1 atm(temperature: room temperature) using a semiconductor parameter analyzer(manufactured by Agilent, 4156C) to which a semi-automatic prober(manufactured by Vector Semiconductor Co., Ltd., AX-2000) was connected.The specific method is as follows.

A voltage of −80 V was applied across the source electrode and the drainelectrode of each organic thin film transistor, the gate voltage waschanged within the range of +20 V to −100 V, and the carrier mobility μ(cm²/Vs) was calculated using the following formula representing a draincurrent I_(d).

I _(d)=(w/2L)μC _(i)(V _(g) −V _(th))²

In the formula, L represents a gate length, w represents a gate width, μrepresents a carrier mobility, C_(i) represents a capacitance of thegate insulating film per unit area, V_(g) represents a gate voltage, andV_(th) represents a threshold voltage.

2. Evaluation of Relative Mobility

The carrier mobility was calculated for each of the ten organic thinfilm transistors produced in each of Examples and Comparative Examples,and the average mobility was determined. Then, the relative mobility wascalculated from the following formula using the average mobility inExample 1 as a reference, and evaluated based on the following criteria.

The relative mobility is preferably as high as possible. In this test,the relative mobility is preferably Rank C or higher, more preferablyRank B or higher, and further preferably Rank A.

Relative mobility=(Average mobility in each of Examples or ComparativeExamples)/(Average mobility in Example 1)

Evaluation Criteria

A: The relative mobility is 1.0 or more.

B: The relative mobility is 0.6 or more and less than 1.0.

C: The relative mobility is 0.2 or more and less than 0.6.

D: The relative mobility is less than 0.2.

3. Evaluation of Variation

The mobility ratio was calculated from the following formula for each ofthe ten organic thin film transistors produced in each of Examples andComparative Examples, and evaluated based on the following criteria.

Mobility ratio=(Highest mobility among ten organic thin filmtransistors)/(Lowest mobility among ten organic thin film transistors)

Evaluation Criteria

A: The mobility ratio is less than 1.5.

B: The mobility ratio is 1.5 or more and less than 1.8.

C: The mobility ratio is 1.8 or more and less than 2.1.

D: The mobility ratio is 2.1 or more.

Table 5 shows the results.

In Table 5, the “Raw material composition” is intended to be acomposition that is used for obtaining the compound represented by theformula (9) in the above-described production method and that includesthe compound represented by the formula (8) and the compound representedby the formula (17) (note that the above composition did not include thecompound represented by the formula (18)). Specifically, for example, inExample 1, “the composition including a compound (1-4)” obtained inSynthesis of composition (raw material composition) of compound (1-4)corresponds to the “raw material composition” herein. In the rawmaterial composition in Example 1, the compound (1-4) corresponds to thecompound represented by the formula (8), and the compound (14)corresponds to the compound represented by the formula (17).

The “Content of compound represented by formula (8)” in the column of“Raw material composition” is intended to be a content (mass %) of thecompound represented by the formula (8) in the raw material compositionrelative to the total solid content of the raw material composition.

The “Content of compound represented by formula (17)” in the column of“Raw material composition” is intended to be a content (mass %) of thecompound represented by the formula (17) in the raw material compositionrelative to the total solid content of the raw material composition.

The synthesis methods in Examples 1 to 7 correspond to the synthesismethod in the first embodiment-1 described above.

TABLE 5 Raw material composition Type and content Type and contentProduct Evaluation of of compound of compound target organic transistorrepresented by represented by (final Yield Relative Table 5 formula (8)formula (17) product) (%) Purity mobility Variation Example 1 Compound98.6% Compound 0.1% or Compound 63.6 A A A (1-4) (1-4′) less (1-1)Example 2 Compound 94.9% Compound 3.0% Compound 61.5 B B B (1-4) (1-4′)(1-1) Example 3 Compound 98.6% Compound 0.1% or Compound 60.1 A A A(1-4) (1-4′) less (3-1) Example 4 Compound 98.6% Compound 0.1% orCompound 62.6 A A A (1-4) (1-4′) less (4-1) Example 5 Compound Compound0.1% or Compound (5-2) 98.1% (5-2′) less (1-1) 61.1 A A A Example 6Compound 98.2% Compound 0.1% or Compound 63.1 A A A (6-2) (6-2′) less(1-1) Example 7 Compound 97.8% Compound 1.0% Compound 60.7 A A A (1-4)(1-4′) (1-1) Comparative Compound — — — Compound 23.5 C C C Example 1(C1-1) (1-1) Comparative Compound — — — Compound 38.3 D D D Example 2(C1-1) (1-1)

As is clear from the results in Table 5, the cyclic imide compoundsobtained by the production methods in Examples are excellent in terms ofyield and purity.

As is also clear from the results in Examples 1 to 7, when the contentof the compound represented by the formula (17), which is an impurity,in the raw material composition is equal to or less than a predeterminedvalue (Examples other than Example 2), the target cyclic imide compoundhas a higher purity.

Furthermore, as is clear from the comparison of Example 1, Example 5,and Example 6, when the compound represented by the formula (8), whichis a raw material component, is the compound represented by the formula(10) (preferably the compound represented by the formula (10′)), thetarget cyclic imide compound is obtained at a higher yield.

Example 8: Production of Compound (8-1)

Synthesis of Compound (8-3)

A composition including the compound (1-4) purified by the same methodas in Example 1 was used. The content of the compound (1-4) in thecomposition including the compound (1-4) was 98.6 mass % relative to thetotal solid content of the composition, and the content of the compound(1-4′) was 0.1 mass % or less relative to the total solid content of thecomposition.

Subsequently, 1.60 g (1.96 mmol) of the composition including thecompound (1-4), 1.65 g (6.85 mmol) of the compound (8-2), and 32 mL ofo-dichlorobenzene were charged into a glass reaction vessel and stirredat 180° C. for 1 hour. After removal of the solvent by distillationunder reduced pressure, the resulting product was purified by silica gelcolumn chromatography to obtain 580 mg (0.674 mmol, yield 34.4%) of acompound (8-3).

Compound (8-3): ¹H NMR (400 MHz, TCE-d², 100° C.): δ 2.87-3.08 (brm, 2H,Ph-CH₂ —CH₂), 3.62-3.75 (brm, 2H, Ph-CH₂-21CH₂ —), 3.82 (s, 3H, CH₃—O-Ph), 3.89 (s, 3H, CH₃ —O—C═O (ester of the Cl₃Ph side)), 3.93-4.08(brm, 3H, CH₃ —O—C═O (ester of the PMB group side)), 4.08-5.55 (brm, 2H,Ph-CH₂ —N), 6.82-7.43 (brm, 9H, ArH), 7.46 (s, 2H, ArH of Cl₃Ph),7.65-8.73 (brm, 1H, ArH), 8.84-9.23 (m, 5H, ArH).

TCE refers to 1,1,2,2-tetrachloroethane.

Synthesis of Compound (8-4)

Into a glass reaction vessel, 300 mg (0.348 mmol) of the compound (8-3),60.8 mg (0.697 mmol) of n-pentylamine, and 3 mL of o-dichlorobenzenewere charged, and reaction was caused at 110° C. for 1 hour. Afterremoval of the solvent by distillation under reduced pressure, theresulting product was dispersed in acetonitrile, collected byfiltration, and dried under reduced pressure to obtain 221 mg (0.307mmol, yield 88.3%) of a compound (8-4).

Compound (8-4): ¹H NMR (400 MHz, TCE-d², 100° C.): δ 0.94 (t, J=6.8 MHz,3H, CH₂—CH₃ ), 1.37-1.45 (m, 4H, N—CH₂—CH₂—(CH₂ )₂—CH₃), 1.78 (q, J=6.8Hz, 2H, N—CH₂—CH₂ —C₃H₇), 2.89-3.10 (brm, 2H, Ph-CH₂ —CH₂), 3.63-3.75(brm, 2H, Ph-CH₂—C{right arrow over (H₂)}—), 3.82 (s, 3H, CH₃ —O-Ph),3.97-4.01 (brm, 3H, CH₃ —O—C═O), 4.19 (t, J=7.2 Hz, 2H, N—CH₂ —C₄H₉),4.30-5.55 (brm, 2H, Ph-CH₂ —N), 6.84-7.41 (brm, 10H, ArH), 8.68-9.57 (m,5H, ArH).

Synthesis of Compound (8-1)

Into a glass reaction vessel, 164 mg (0.228 mmol) of the compound (8-4),8.6 mL of o-dichlorobenzene, and 54.8 mg (0.570 mmol) of methanesulfonicacid were charged, and stirring was performed at 150° C. for 3 hours.After cooling with water, the resulting mixture was filtered and driedunder reduced pressure. The obtained solid was purified by sublimationto obtain 35 mg (0.0618 mmol, yield 27.1%) of a compound (8-1).

Compound (8-1): ¹H NMR (400 MHz, TCE-d², 100° C.): δ 0.94 (t, J=7.0 Hz,3H, —CH₂—CH₃ ), 1.44-1.40 (m, 4H, N—CH₂—CH₂—(CH₂ )₂—CH₃), 1.79 (q, 2H,J=7.2 Hz, N—CH₂—CH₂ —C₃H₇), 3.07 (t, J=7.8 Hz, 2H, Ph-CH₂ —), 4.20 (t,J=7.4 Hz, 2H, N—CH₂ —C₄H₉), 4.45 (t, J=7.8 Hz, 2H, Ph-CH₂—CH₂ —),7.34-7.18 (m, 5H, ArH of phenyl), 8.84 (d, J=7.6 Hz, 2H, ArH), 9.27 (d,J=8.0 Hz, 2H, ArH), 9.64 (s, 2H, ArH).

Example 9

Synthesis of Compound (9-2)

A compound (8-1) was obtained in the same manner as in Example 8, exceptthat the compound (9-1) was used instead of the compound (8-2), andphenethylamine was used instead of the pentylamine.

Example 10

Production of Compound (10-1)

A compound (10-1) was obtained in the same manner as in Example 8,except that octylamine was used instead of the pentylamine.

Compound (10-2): ¹H NMR (400 MHz, TCE-d², 100° C.): δ 0.83 (t, J=6.6MHz, 3H, CH₂—CH₃ ), 1.19-1.38 (m, 10H, CH₂—(CH₂ )₅—CH₃), 1.69 (q, J=6.4Hz, 2H, N—CH₂—CH₂ —C₆H₁₃), 2.85-3.14 (m, 2H, Ph-CH₂ —CH₂), 3.53-3.74 (m,2H, Ph-CH₂—CH₂ —), 3.79-3.83 (m, 3H, CH₃ —O-Ph), 3.92-4.02 (m, 3H, CH₃—O—C═O), 4.13 (t, J=7.2 Hz, 2H, N—CH₂ —C₇H₁₅), 4.31-5.24 (m, 2H, Ph-CH₂—N), 6.87-7.41 (m, 9H, ArH), 7.53-8.20 (m, 1H, ArH), 8.64-9.47 (m, 5H,ArH).

Compound (10-1): ¹H NMR (400 MHz, TCE-d², 100° C.): δ 0.88 (t, J=7.0 Hz,3H, CH₂—CH₃ ), 1.50-1.30 (m, 10H, N—CH₂—CH₂—(CH₂ )₅—CH₃), 1.78 (q, J=7.2Hz, 2H, N—CH₂—CH₂ —C₆H₁₃), 3.07 (t, J=7.8 Hz, 2H, Ph-CH₂ —), 4.19 (t,J=7.4 Hz, 2H, N—CH₂ —C₇H₁₅), 4.44 (t, J=7.8 Hz, 2H, Ph-CH₂—CH₂ —),7.18-7.34 (m, 5H, ArH of phenyl), 8.85 (d, J=7.6 Hz, 2H, ArH), 9.28 (d,J=8.0 Hz, 2H, ArH), 9.64 (s, 2H, ArH).

Evaluation

“Analysis of purity by liquid chromatography” and “Production andevaluation of organic thin film transistor” were performed in the samemanner as in Example 1 using the compounds obtained by the productionmethods in Examples 8 to 10. Table 6 shows the results.

In Table 6, the “Raw material composition” is intended to be acomposition that is used for obtaining the compound represented by theformula (9) in the above-described production method and that includesthe compound represented by the formula (8) and the compound representedby the formula (17) (note that the above composition did not include thecompound represented by the formula (18)). Specifically, “thecomposition including a compound (1-4)” in Examples 8 to 10 correspondsto the “raw material composition” herein. In the raw materialcompositions in Examples 8 to 10, the compound (1-4) corresponds to thecompound represented by the formula (8), and the compound (1-4′)corresponds to the compound represented by the formula (17).

The “Content of compound represented by formula (8)” in the column of“Raw material composition” is intended to be a content (mass %) of thecompound represented by the formula (8) in the raw material compositionrelative to the total solid content of the raw material composition.

The “Content of compound represented by formula (17)” in the column of“Raw material composition” is intended to be a content (mass %) of thecompound represented by the formula (17) in the raw material compositionrelative to the total solid content of the raw material composition.

The numerical value in the column of “yield” refers to a yield of afinal target compound (e.g., the compound (8-1) in Example 8) relativeto the compound (1-4).

The production methods in Examples 8 to 10 correspond to the productionmethod in the above-described second embodiment.

TABLE 6 Raw material composition Type and content Type and contentProduct Evaluation of of compound ofc ompound (final organic transistorrepresented by represented by target Yield Relative Table 6 formula (8)formula (17) product) (%) purity mobility Variation Example 8 Compound98.6% Compound 0.1% or Compound 8.23 A A A (1-4) (1-4′) less (8-1)Example 9 Compound 98.6% Compound 0.1% or Compound 7.21 A A A (1-4)(1-4′) less (8-1) Example 10 Compound 98.6% Compound 0.1% or Compound8.19 A B A (1-4) (1-4′) less (10-1)

Furthermore, the following derivatives can be synthesized by using theproduction method according to an embodiment of the present invention.

Example 11

Synthesis of Compound (11-2)

Into a glass reaction vessel, 1 g (1.14 mmol) of the compositionincluding the compound (1-4) and prepared in Example 1, 25.5 mg (0.114mmol) of palladium acetate, 205 mg (0.567 mmol) of copper(II)trifluoromethanesulfonate, 609 mg (3.42 mmol) of N-bromosuccinimide, 33mL of 1,1,2-trichloroethane, and 5 mL of N,N-dimethylformamide werecharged, and reaction was caused in a nitrogen atmosphere at 60° C. for2 hours. The resulting product was allowed to cool to room temperatureand poured into 80 mL of methanol. The precipitated solid was collectedby filtration. The obtained solid was purified by silica gel columnchromatography to obtain 0.887 g (0.910 mmol, yield 79.8%) of a compound(11-2).

Compound (11-2): ¹H NMR (CDCl₃) δ 3.95 (6H, s), 7.48 (4H, s), 9.18 (2H,s), 9.27 (2H, s)

Synthesis of Compound (11-3)

Into a glass reaction vessel, 224 mg (0.229 mmol) of the compound(11-2), 370 g (4.13 mmol) of copper cyanide, and 9.2 mL ofN,N-dimethylformamide were charged, and reaction was caused in anitrogen atmosphere at 100° C. for 1 hour. The resulting product wasallowed to cool to room temperature and then added to 200 mL ofmethanol. The precipitated solid was collected by filtration. Theobtained solid was purified by silica gel column chromatography toobtain 168 mg (0.194 mmol, yield 84.7%) of a compound (11-3).

Compound (11-3): ¹H NMR (CDCl₃) δ 3.99 (6H, s), 7.51 (4H, s), 9.16 (2H,s), 9.45 (2H, s)

Production of Compound (11-1)

Into a glass reaction vessel, 140 mg (0.161 mmol) of the compound(11-3), 45.8 mg (0.354 mmol) of octylamine, and 5.6 mL ofo-dichlorobenzene were charged, and reaction was caused in a nitrogenatmosphere at 150° C. for 6 hours. After cooling, the resulting productwas collected by filtration. The obtained solid was purified by silicagel column chromatography to obtain 60.3 mg (0.0905 mmol, yield 56.2%)of a compound (11-1).

Compound (11-1): ¹H NMR (TCE-d², 100° C.) δ 0.90 (t, J=7.0 Hz, 6H),1.25-1.48 (m, 20H), 1.78 (m, 4H), 4.23 (t, J=7.8 Hz, 4H), 9.12 (s, 2H),9.37 (s, 2H)

Example 12

Synthesis of Compound (12-3)

Into a glass reaction vessel, 0.900 g (0.923 mmol) of the compound(11-2), 0.863 g (2.31 mmol) of the compound (12-2), 0.0472 g (0.0923mmol) of bis(tri-tert-butylphosphine)palladium(0), 0.0352 g (0.185 mmol)of copper(I) iodide, and 46 mL of tetrahydrofuran were charged, andreaction was caused in a nitrogen atmosphere at 60° C. for 1 hour. Aftercooling to room temperature, 100 mL of methanol was added thereto. Theprecipitated solid was collected by filtration. The obtained solid waspurified by silica gel column chromatography to obtain 0.853 g (0.868mmol, yield 94.0%) of a compound (12-3).

Compound (12-3): ¹H NMR (CDCl₃) δ 3.89 (6H, s), 7.44 (4H, s), 7.57 (2H,d, J=4 Hz), 7.99 (2H, d, J=4 Hz), 8.77 (2H, s), 9.07 (2H, s)

Synthesis of Compound (12-1)

Into a glass reaction vessel, 0.620 g (0.630 mmol) of the compound(12-3), 0.384 g (3.15 mmol) of phenethylamine, and 31 mL ofo-dichlorobenzene were charged, and reaction was caused at 80° C. for 2hours. The resulting product is allowed to cool to room temperature,then added to 100 mL of methanol cooled with ice, and stirred undercooling with ice for 20 minutes. The precipitated solid was collected byfiltration and dried under reduced pressure to obtain 0.452 g (0.590mmol, yield 93.7%) of a compound (12-1).

Compound (12-1): ¹H NMR (CDCl₃) δ 3.02-3.06 (4H, m), 4.40-4.44 (4H, m),7.23-7.34 (10H, m), 7.67 (2H, d, J=4 Hz), 8.04 (2H, d, J=4 Hz), 8.92(2H, s), 9.27 (2H, s)

Example 13

Synthesis of Compound (13-3)

Into a glass reaction vessel, 50 mg (0.0513 mmol) of the compound(11-2), 23.4 mg (0.128 mmol) of the compound (13-2), 0.977 mg (0.00513mmol) of copper(I) iodide, 26.0 mg (0.257 mmol) of triethylamine, and2.5 mL of tetrahydrofuran were charged, and reaction was caused in anitrogen atmosphere at 60° C. for 1 hour. The resulting product wasallowed to cool to room temperature and then poured into 5 mL ofmethanol. The precipitated solid was collected by filtration. Theobtained solid was purified by silica gel column chromatography toobtain 35 mg (0.0306 mmol, yield 59.7%) of a compound (13-3).

Compound (13-3): ¹H NMR (CDCl₃) δ 1.22-1.26 (42H, m), 3.96 (6H, s), 7.47(4H, s), 9.03 (2H, s), 9.12 (2H, s)

Synthesis of Compound (13-1)

Into a glass reaction vessel, 35 mg (0.0306 mmol) of the compound(13-3), 15.3 mg (0.0918 mmol) of the compound (13-4), and 1.7 mL ofo-dichlorobenzene were charged, and reaction was caused in a nitrogenatmosphere at 100° C. for 1 hour. The resulting product was allowed tocool to room temperature and then poured into 17 mL of methanol. Theprecipitated solid was collected by filtration. The obtained solid waspurified by silica gel column chromatography to obtain 15.0 mg (0.0143mmol, yield 46.6%) of a compound (13-1).

Compound (13-1): ¹H NMR (CDCl₃) δ 1.22-1.35 (42H, m), 3.77 (6H, s), 3.87(6H, s), 5.40 (4H, s), 6.42 (2H, d, J=10 Hz), 6.48 (2H, s), 7.15 (2H, d,J=10 Hz), 8.98 (2H, s), 9.69 (2H, s)

Among the compounds (11-1), (12-1), and (13-1), the compound (11-1) wasevaluated for transistor characteristics in the same manner as inExample 1. As a result, the compound (11-1) was confirmed to have thesame transistor characteristics as those of the compound (1-1).

Examples 14 to 19

The compound represented by the formula (2) could also be synthesizedfrom the following compounds in the same manner as in Example 1. InExamples 14 to 19, it was found that the solubility of the raw materialswas improved, which provides synthetic advantages such as reducing theamount of reaction solvents. The following synthetic methods are thesame as the synthetic method in Example 1, except that the compoundserving as a starting material is different, and only the results areshown.

As is clear from the comparison of the results in Examples 14 to 19 andExamples 1, 5, and 6, the yield is better when the number of carbonatoms of the aliphatic hydrocarbon group in the compound represented bythe formula (8) (or the compound represented by the formula (11A)) is 2or more.

Example 14 Synthesis of Compound (1-1)

Compound (1-1): yield 470 mg (0.782 mmol, yield 64.1%)

Example 15 Synthesis of Compound (1-1)

Compound (1-1): 471 mg (0.784 mmol, yield 64.3%)

Example 16 Synthesis of Compound (1-1)

Compound (1-1): yield 469 mg (0.779 mmol, yield 63.9%)

Example 17 Synthesis of Compound (1-1)

Compound (1-1): yield 470 mg (0.781 mmol, yield 64.0%)

Example 18 Synthesis of Compound (1-1)

Compound (1-1): yield 468 mg (0.778 mmol, yield 63.8%)

Example 19 Synthesis of Compound (1-1)

Compound (1-1): yield 465 mg (0.775 mmol, yield 63.5%)

Example 20

The compound represented by the formula (2) could also be synthesizedfrom the following compounds in the same manner as in Example 8. Thefollowing synthetic methods are the same as the synthetic method inExample 8, except that the compound serving as a starting material isdifferent, and only the results are shown.

As is clear from the comparison of the results in Example 20 and Example8, the yield is better when the number of carbon atoms of the aliphatichydrocarbon group in the compound represented by the formula (8) (or thecompound represented by the formula (11A)) is 2 or more.

Compound (8-1): yield 36.1 mg (0.0637 mmol, yield 8.50% relative to thecompound (14-1))

REFERENCE SIGNS LIST

-   -   1 substrate    -   2 gate electrode    -   3 gate insulating film    -   4A source electrode    -   4B drain electrode    -   5 organic semiconductor film (organic semiconductor layer)    -   6 sealing layer    -   10, 20 organic thin film transistor (organic TFT)    -   41 coating liquid    -   42 substrate    -   43 member

What is claimed is:
 1. A compound represented by formula (4) below,

wherein in the formula (4), A¹¹ to A¹⁸ each independently represent —N═or —C(R⁵)═, R¹⁵ represents a hydrogen atom or a substituent, at leastone of A¹¹ to A¹⁸ represents —N═, R¹² to R¹⁴ each independentlyrepresent an aliphatic hydrocarbon group, an aryl group, or a heteroarylgroup, one of R¹² and R¹³ represents an aliphatic hydrocarbon group andthe other represents an aryl group or a heteroaryl group, R³¹ representsa substituent, and P³¹ represents a protecting group.
 2. A compoundrepresented by formula (6) below,

wherein in the formula (6), A¹¹ to A¹⁸ each independently represent —N═or —C(R¹⁵)═, R¹⁵ represents a hydrogen atom or a substituent, at leastone of A¹¹ to A¹⁸ represents —N═, R¹⁴ represents an aliphatichydrocarbon group, an aryl group, or a heteroaryl group, R³¹ and R⁵¹each independently represent a substituent, and P³¹ represents aprotecting group.
 3. A compound represented by formula (7) below,

wherein in the formula (7), A¹¹ to A¹⁸ each independently represent —N═or —C(R¹⁵)═, R¹⁵ represents a hydrogen atom or a substituent, at leastone of A¹¹ to A¹⁸ represents —N═, R¹⁴ represents an aliphatichydrocarbon group, an aryl group, or a heteroaryl group, and R³¹ and R⁵¹each independently represent a substituent.
 4. A compound represented byformula (11A′) below,

wherein in the formula (11A′), X⁵ to X⁸ each independently represent—CO—O—R¹⁰¹, each R¹⁰¹ independently represents an aliphatic hydrocarbongroup, an aryl group, or a heteroaryl group, R¹⁰¹ in X⁵ and R¹⁰¹ in X⁸are different from each other, one of R¹⁰¹ in X⁵ and R¹⁰¹ in X⁸represents an aliphatic hydrocarbon group and the other represents anaryl group or a heteroaryl group, R¹⁰¹ in X⁶ and R¹⁰¹ in X⁷ aredifferent from each other, one of R¹⁰¹ in X⁶ and R¹⁰¹ in X⁷ representsan aliphatic hydrocarbon group and the other represents an aryl group ora heteroaryl group, and R⁸¹ to R⁸⁶ each independently represent ahydrogen atom or a substituent, and at least one of R⁸¹ to R⁸⁶ is asubstituent.
 5. A compound represented by formula (11A″) below,

wherein in the formula (11A″), X⁵ to X⁸ each independently represent—CO—O—R¹⁰¹; each R¹⁰¹ independently represents an aliphatic hydrocarbongroup, an aryl group, or a heteroaryl group; R¹⁰¹ in X⁵ and R¹⁰¹ in X⁸are different from each other; one of R¹⁰¹ in X⁵ and R¹⁰¹ in X⁸represents an aliphatic hydrocarbon group and the other represents anaryl group or a heteroaryl group; R¹⁰¹ in X⁶ and R¹⁰¹ in X⁷ aredifferent from each other; one of R¹⁰¹ in X⁶ and R¹⁰¹ in X⁷ representsan aliphatic hydrocarbon group and the other represents an aryl group ora heteroaryl group; when the aliphatic hydrocarbon group represented byR¹⁰¹ is an aliphatic hydrocarbon group having one carbon atom, the arylgroup represented by R¹⁰¹ is an unsubstituted aryl group or an arylgroup into which one or two substituents are introduced; and R⁸³ to R⁸⁶each independently represent a hydrogen atom or a substituent.